Flame-retardant antibacterial wave-absorbing PET (Polyethylene Terephthalate) fiber and preparation method thereof

Abstract

The invention discloses a flame-retardant antibacterial wave-absorbing PET fiber and a preparation method thereof.The fiber comprises a fiber body and an antibacterial wave-absorbing layer arranged on the surface of the fiber body, and the fiber body is of a skin-core composite structure and sequentially comprises a core layer and a flame-retardant wave-absorbing barrier layer from inside to outside; the raw material of the flame-retardant and wave-absorbing barrier layer is a flame-retardant and wave-absorbing mixture and comprises the following components in parts by weight: 100 parts of PET polyester chips, 9-15 parts of a flame retardant, 22-40 parts of flame-retardant and wave-absorbing particles and 1.5-4 parts of a compatilizer. The antibacterial and wave-absorbing layer can provide excellent electromagnetic wave absorbing capacity through the antibacterial and wave-absorbing particles in the antibacterial and wave-absorbing layer, electromagnetic pollution can be effectively prevented, and meanwhile excellent antibacterial performance can be provided through active oxygen generated under illumination and / or electromagnetic wave irradiation. The flame-retardant and wave-absorbing barrier layer can improve the flame-retardant performance through flame-retardant and wave-absorbing particles in the flame-retardant and wave-absorbing barrier layer, and also can provide good electromagnetic wave reflecting and absorbing capabilities.

Description

Technical Field

[0001] The present invention relates to the field of polyester fiber materials, and in particular to a flame-retardant and antibacterial wave-absorbing PET fiber and a preparation method thereof. Background Art

[0002] PET fiber (polyester, polyethylene terephthalate), commonly known as "polyester," has advantages such as high breaking strength and elastic modulus, moderate resilience, excellent heat setting, good abrasion resistance, and stable chemical properties. It is widely used in the manufacture of home textiles and industrial textiles.

[0003] Ordinary polyester fibers are flammable. Adding flame-retardant ingredients can improve their flame retardancy, thereby enhancing the safety of the fibers. For example, patent CN112831863B discloses a flame-retardant polyester fiber and its preparation process, and patent CN109881289B discloses a method for preparing flame-retardant and smoke-suppressing PET fibers.

[0004] However, with the enrichment and expansion of polyester fiber application scenarios, more and more requirements are placed on the functions of polyester fibers, such as electromagnetic shielding performance and antibacterial properties.

[0005] With the popularization of electronic devices, the harm caused to the human body by electromagnetic waves in daily life has attracted more and more attention. Therefore, the research and development of electromagnetic protection materials with electromagnetic wave shielding properties to reduce radiation and strengthen human body protection has important significance and application prospects. Ferroferric oxide has high saturation magnetization, coercive force and high resistivity, which can play a role in magnetic permeability loss to electromagnetic waves. In addition, the abundance of ferroferric oxide raw materials is high, the cost is low, and the synthesis method is simple, making it a commonly used magnetic loss type absorbing material. For example, patent CN118727436B discloses a magnetic composite fiber cloth with electromagnetic shielding effect and its preparation method, which proposes to modify the fiber cloth with ferroferric oxide to give it electromagnetic wave shielding performance. However, the loss mechanism of the absorbing material made of a single material is simple, the absorbing efficiency is low, and it is difficult to meet the use requirements.

[0006] Antibacterial polyester fibers can effectively reduce bacterial growth and harm to human health. Traditionally, antibacterial properties are achieved by adding antibacterial agents, such as silver or copper. For example, patent CN105401245B discloses a method for preparing copper oxide antibacterial fibers. However, uneven dispersion of the antibacterial agent within the fiber can affect its antibacterial properties and also compromise fiber strength.

[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 a flame-retardant and antibacterial absorbing PET fiber and a preparation method thereof in view of the deficiencies in the above-mentioned prior art.

[0009] To solve the above technical problems, the present invention adopts the following technical solutions: providing a flame-retardant and antibacterial absorbing PET fiber, comprising a fiber body and an antibacterial absorbing layer disposed on the surface of the fiber body. The fiber body is a skin-core composite structure, comprising, from the inside out, a core layer and a flame-retardant absorbing barrier layer. The flame-retardant absorbing barrier layer is made of a flame-retardant absorbing mixture comprising, by weight, the following components: 100 parts of PET polyester chips, 9-15 parts of a flame retardant, 22-40 parts of flame-retardant absorbing particles, and 1.5-4 parts of a compatibilizer.

[0010] The flame retardant and wave absorbing particles are prepared by the following steps:

[0011] S1-1, preparing carboxylated graphene oxide;

[0012] S1-2, loading zinc oxide hybridized ferroferric oxide on carboxylated graphene oxide to obtain composite wave-absorbing particles;

[0013] S1-3, performing polyaniline hybridization treatment on the composite wave-absorbing particles to obtain flame-retardant wave-absorbing particles;

[0014] The antibacterial absorbing layer is obtained by coating the surface of the fiber body with antibacterial absorbing particles. The preparation method of the antibacterial absorbing particles includes the following steps:

[0015] S2-1. Preparation of partially oxidized Ti3C2T X MXene;

[0016] S2-2, preparation of Ni hybrid carbon dots;

[0017] S2-3, partially oxidize Ti3C2T x MXene and Ni-hybridized carbon dots self-assemble to obtain antibacterial and wave-absorbing particles.

[0018] Preferably, the fiber body is prepared by a core-skin composite spinning process using PET polyester chips as the core material and a flame retardant and wave absorbing mixture as the skin material;

[0019] The antibacterial absorbing layer is obtained by coating the antibacterial absorbing particles on the surface of the fiber body through an impregnation process. The specific impregnation process is as follows:

[0020] The antibacterial absorbing particles are dispersed in deionized water to obtain an antibacterial absorbing particle dispersion; the fiber body is ultrasonically washed in deionized water, taken out and dried, immersed in the antibacterial absorbing particle dispersion, taken out and dried, completing one immersion, and the immersion is repeated several times to form an antibacterial absorbing layer on the surface of the fiber body.

[0021] Preferably, the dipping process used to prepare the antibacterial absorbing layer is:

[0022] The antibacterial absorbing particles are added to deionized water and ultrasonically dispersed for 1-4 hours to prepare an antibacterial absorbing particle dispersion with a concentration of 5-20 mg / mL; the fiber body is ultrasonically washed in deionized water for 0.5-2 hours, taken out and dried at 80-120°C for 1-4 hours, placed in the antibacterial absorbing particle dispersion, immersed at 50-70°C for 10-30 minutes, taken out and dried at 80-120°C for 1-4 hours to complete one immersion, and the immersion is repeated 2-8 times to form an antibacterial absorbing layer on the surface of the fiber body.

[0023] Preferably, the flame retardant and wave absorbing particles are prepared by the following steps:

[0024] S1-1, adding graphene oxide to a mixture of H2O2 and nitric acid, stirring and refluxing under heating, filtering, washing with deionized water until neutral, and drying to obtain carboxylated graphene oxide;

[0025] S1-2. Carboxylated graphene oxide and urea are added to deionized water and ultrasonically dispersed to obtain a graphene dispersion; PVP, FeCl2, FeCl3, and ZnSO4 are added to a mixed solvent consisting of deionized water and ethylene glycol in a volume ratio of 1:1, and stirred. The resulting mixture is added to the graphene dispersion while stirring, and the resulting product is transferred to a reactor, reacted at 190-240° C. for 6-24 hours, centrifuged, washed, and vacuum dried to obtain composite absorbing particles;

[0026] S1-3. Disperse the composite absorbing particles in deionized water, add aniline, stir, add ammonium persulfate, adjust the pH of the reaction system to 2-3, stir the reaction, centrifuge, wash, and vacuum dry to obtain flame-retardant absorbing particles.

[0027] Preferably, the flame retardant and wave absorbing particles are prepared by the following steps:

[0028] S1-1. Take 2 g of graphene oxide and add it to a mixture of 50 mL of 20 wt% H2O2 and 100 mL of 60 wt% nitric acid. Stir and reflux at 80°C for 6 h. Filter, wash with deionized water until neutral, and dry to obtain carboxylated graphene oxide.

[0029] S1-2, take 1g of carboxylated graphene oxide and 4.5g of urea, add them to 100mL of deionized water, and ultrasonically disperse them for 1h to obtain a graphene dispersion; add 1g of PVP, 0.381g of FeCl2, 0.972g of FeCl3, and 0.322g of ZnSO4 to 100mL of a mixed solvent consisting of deionized water and ethylene glycol in a volume ratio of 1:1, and stir for 15min. The resulting mixture is added to the graphene dispersion under stirring and stirred for 1h. The resulting product is transferred to a reactor, reacted at 220°C for 12h, centrifuged, washed, and vacuum dried to obtain composite absorbing particles;

[0030] S1-3. 0.2 g of the composite absorbing particles was added to 100 mL of deionized water and ultrasonically dispersed for 45 min. 0.35 g of aniline was added and stirred for 1 h. 0.85 g of ammonium persulfate was added at 5° C. The pH of the reaction system was adjusted to 2 with 30 wt % hydrochloric acid. The mixture was stirred and reacted at room temperature for 8 h. The mixture was centrifuged, washed, and vacuum dried to obtain flame-retardant absorbing particles.

[0031] Preferably, the antibacterial wave-absorbing particles are prepared by the following steps:

[0032] S2-1, Ti3C2T X MXene was calcined at 250-400 °C for 2-4 h in air atmosphere and ground to obtain partially oxidized Ti3C2T x MXene;

[0033] S2-2, adding nickel sulfate hexahydrate, glucose, polyethyleneimine, dithiodibenzoic acid and 4-methoxypyridine to deionized water, stirring, adjusting the pH to 9, heating and stirring to react, transferring the resulting precursor to a reactor, reacting at 230-250° C. for 5-20 h, centrifuging, washing, and vacuum drying to obtain Ni hybrid carbon dots;

[0034] S2-3, adding Ni hybrid carbon dots to hydrochloric acid, ultrasonicating, filtering, washing the solid product with deionized water until neutral, and then dispersing it in deionized water to obtain a carbon dot dispersion; partially oxidizing Ti3C2T x MXene is dispersed in deionized water to obtain a MXene dispersion;

[0035] The carbon dot dispersion was added to the MXene dispersion under stirring, and the mixture was continuously stirred, allowed to stand, filtered, washed, and freeze-dried to obtain antibacterial and wave-absorbing particles.

[0036] Preferably, the antibacterial wave-absorbing particles are prepared by the following steps:

[0037] S2-1, Ti3C2T XMXene was calcined at 350 °C for 3 h in air atmosphere and ground to obtain partially oxidized Ti3C2T x MXene;

[0038] S2-2, 524 mg of nickel sulfate hexahydrate, 600 mg of glucose, 350 mg of polyethyleneimine, 306 mg of dithiodibenzoic acid, and 218 mg of 4-methoxypyridine were added to 150 mL of deionized water and stirred for 30 min. Then, the pH was adjusted to 9 with 1 mol / L sodium hydroxide solution, and the mixture was stirred and reacted at 60°C for 4 h. The resulting precursor was transferred to a reactor and reacted at 230°C for 10 h. The mixture was centrifuged, washed, and dried in vacuo to obtain Ni-hybridized carbon dots: Ni-CDs;

[0039] S2-3, 1.5 g Ni hybrid carbon dots were added to 80 mL 1 mol / L hydrochloric acid, ultrasonically treated at 60 ° C for 1 h, filtered, and the solid product was washed with deionized water until neutral, then added to 50 mL deionized water and ultrasonically dispersed for 1.5 h to obtain a carbon dot dispersion; 1 g partially oxidized Ti3C2T x MXene was added to 50 mL of deionized water and ultrasonically dispersed for 2 h to obtain a MXene dispersion;

[0040] The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 1000 rpm for 10 h. Then, the mixture was allowed to stand for 2 h, filtered, washed, and freeze-dried to obtain antibacterial absorbing particles.

[0041] Preferably, the compatibilizer is one or more of EEA (ethylene-ethyl acrylate), EVA (ethylene-vinyl acetate copolymer), and maleic anhydride grafted polyolefin elastomer (maleic anhydride grafted POE);

[0042] The flame retardant is one or more of ammonium polyphosphate, trihydroxyethyl phosphate, phenylphosphonic acid, and trihydroxymethylphosphine oxide.

[0043] The present invention also provides a method for preparing the flame-retardant and antibacterial absorbing PET fiber as described above, comprising the following steps:

[0044] Step 1: Evenly mix PET polyester chips, flame retardant, flame retardant and wave-absorbing particles, and a compatibilizer to obtain a flame retardant and wave-absorbing mixture;

[0045] Step 2: Adding PET polyester chips as the core layer material and the flame retardant and microwave absorbing mixture as the skin layer material to their respective corresponding screw extruders for melt extrusion, and then adopting a skin-core composite spinning process to prepare a fiber body;

[0046] Step 3: The antibacterial and antibacterial absorbing particles are impregnated on the surface of the fiber body to form an antibacterial and antibacterial absorbing layer, thereby finally obtaining the flame-retardant and antibacterial absorbing PET fiber.

[0047] Preferably, in step 2, the mass ratio of the skin layer raw material to the core layer raw material is 1:9 to 3.5:6.5; the melt extrusion temperature corresponding to the core layer raw material is 260-290°C, and the melt extrusion temperature corresponding to the skin layer raw material is 250-290°C;

[0048] The spinning process parameters are: spinning temperature 260-280°C, spinning speed 2000-4500m / min, side blowing temperature 10-30°C, and side blowing speed 0.2-1m / s.

[0049] The beneficial effects of the present invention are:

[0050] The present invention provides a flame-retardant and antibacterial absorbing PET fiber having a multilayer composite structure formed by, from the inside out, a core layer, a flame-retardant and antibacterial absorbing barrier layer, and an antibacterial absorbing layer. The antibacterial absorbing layer can provide excellent electromagnetic wave absorption capabilities through the antibacterial absorbing particles therein, effectively protecting against electromagnetic pollution, and can also provide excellent antibacterial properties through the active oxygen generated under light and / or electromagnetic wave irradiation. In addition to improving the flame retardancy, the flame-retardant and antibacterial absorbing barrier layer can also provide good electromagnetic wave reflection and absorption capabilities through the flame-retardant and antibacterial absorbing particles therein. This allows the portion of the incident electromagnetic wave not absorbed by the antibacterial absorbing layer to be absorbed and reflected by the flame-retardant and antibacterial absorbing barrier layer, thereby enabling multiple reflections and absorptions between the antibacterial absorbing layer and the flame-retardant and antibacterial absorbing barrier layer, ultimately significantly improving the electromagnetic wave shielding capability and reducing the amount of electromagnetic wave transmission. Furthermore, the flame-retardant, absorbing barrier layer, through its antibacterial, absorbing particles, can block reactive oxygen species generated within the layer, preventing them from entering the core layer and causing degradation of the polyester therein. Furthermore, the flame-retardant, absorbing barrier layer improves the fiber's mechanical strength and antistatic properties.

[0051] The Ni hybridized carbon dots in the antibacterial wave-absorbing layer of the present invention can not only absorb electromagnetic waves, but also generate active oxygen with antibacterial ability under the action of electromagnetic waves, which is beneficial to the use effect of the fiber; the antibacterial wave-absorbing particles of the present invention are formed by the Ni hybridized carbon dots and the partially oxidized Ti3C2T x The combination of MXene enables the antibacterial absorbing layer on the fiber surface prepared using it to produce active oxygen with antibacterial ability under light or electromagnetic wave irradiation, which can give the fiber excellent antibacterial and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 The infrared absorption spectrum of the flame retardant and wave absorbing particles prepared in Example 1;

[0053] Figure 2 The infrared absorption spectrum of the antibacterial wave-absorbing particles prepared in Example 1;

[0054] Figure 3 This is the electromagnetic shielding performance test result;

[0055] Figure 4 It is the test result of total shielding effectiveness degradation rate;

[0056] Figure 5 is the limiting oxygen index test result;

[0057] Figure 6 The antibacterial performance test results of the antibacterial wave-absorbing particles;

[0058] Figure 7 The antibacterial performance test results of the fiber;

[0059] Figure 8 The singlet oxygen generation ability test results of the antibacterial wave-absorbing particles prepared in Example 1 under different conditions;

[0060] Figure 9 The singlet oxygen generation ability test results of the antibacterial wave-absorbing particles prepared in Examples 1-4 and Comparative Examples 4-6 are shown;

[0061] Figure 10 The results of the breaking strength test. DETAILED DESCRIPTION

[0062] The present invention is further described in detail below with reference to the embodiments so that those skilled in the art can implement the invention with reference to the description.

[0063] It should be understood that terms such as “having”, “including” and “comprising” used herein do not preclude the existence or addition of one or more other elements or combinations thereof.

[0064] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Materials and reagents used in the following examples are commercially available unless otherwise specified. In the following examples, where specific conditions are not specified, the experiments were conducted under conventional conditions or those recommended by the manufacturer. Reagents and instruments used, where the manufacturer is not specified, are commercially available conventional products.

[0065] The present invention provides a flame-retardant and antibacterial absorbing PET fiber, which is characterized by comprising a fiber body and an antibacterial absorbing layer arranged on the surface of the fiber body. The fiber body is a skin-core composite structure, and comprises, from the inside to the outside, a core layer and a flame-retardant and absorbing barrier layer. The raw material of the flame-retardant and absorbing barrier layer is a flame-retardant and absorbing mixture, which comprises the following components by weight: 100 parts of PET polyester chips, 9-15 parts of a flame retardant, 22-40 parts of flame-retardant and absorbing particles, and 1.5-4 parts of a compatibilizer.

[0066] In the present invention, the flame retardant and wave absorbing particles are prepared by the following steps:

[0067] S1-1. Preparation of carboxylated graphene oxide:

[0068] 1-4 g of graphene oxide was added to a mixture of 25-100 mL of 20 wt% H2O2 and 50-200 mL of 60 wt% nitric acid, stirred and refluxed at 70-90°C for 3-12 hours, filtered, washed with deionized water until neutral, and dried to obtain carboxylated graphene oxide;

[0069] S1-2, loading zinc oxide hybridized ferroferric oxide on carboxylated graphene oxide to obtain composite wave-absorbing particles:

[0070] 0.5-2 g of carboxylated graphene oxide and 2.2-9 g of urea are added to 50-200 mL of deionized water and ultrasonically dispersed for 0.5-2 h to obtain a graphene dispersion; 0.5-2 g of PVP, 0.2-0.6 g of FeCl2, 0.5-2 g of FeCl3, and 0.15-0.65 g of ZnSO4 are added to 50-200 mL of a mixed solvent consisting of deionized water and ethylene glycol in a volume ratio of 1:1, and stirred for 5-30 min. The resulting mixture is added to the graphene dispersion under stirring and stirred for 0.5-2 h. The resulting product is transferred to a reactor, reacted at 190-240 ° C for 6-24 h, centrifuged, washed, and vacuum dried to obtain composite absorbing particles;

[0071] S1-3, performing polyaniline hybridization treatment on the composite wave-absorbing particles to obtain flame-retardant wave-absorbing particles:

[0072] 0.1-0.4 g of the composite absorbing particles were added to 50-200 mL of deionized water, and ultrasonically dispersed for 30-90 min. 0.15-0.7 g of aniline was added, and the mixture was stirred for 0.5-2 h. 0.4-1.7 g of ammonium persulfate was added at 2-10° C., and the pH of the reaction system was adjusted to 2-3 with 30 wt % hydrochloric acid. The mixture was stirred and reacted at room temperature for 4-16 h. The mixture was centrifuged, washed, and vacuum dried to obtain flame retardant absorbing particles.

[0073] In the present invention, the antibacterial absorbing layer is obtained by coating the surface of the fiber body with antibacterial absorbing particles. The preparation method of the antibacterial absorbing particles includes the following steps:

[0074] S2-1. Preparation of partially oxidized Ti3C2T X MXene:

[0075] Ti3C2T X MXene was calcined at 250-400 °C for 2-4 h in air atmosphere and ground to obtain partially oxidized Ti3C2T x MXene;

[0076] Among them, Ti3C2T X MXene can be a conventional commercial product or can be prepared by a conventional etching method. For example, in some embodiments, the following method is used to prepare MXene: 1.35 g of LiF is added to 25 mL of a 9 M HCl solution and stirred for 30 min to obtain an etching solution; 2 g of Ti3AlC2 is added to the etching solution, and the mixture is stirred at 45°C for 48 h. After the reaction is completed, the product is centrifuged and washed with deionized water until the supernatant has a pH of 6, and then dried in a vacuum at 60°C for 12 h to obtain Ti3C2T X MXene;

[0077] S2-2. Preparation of Ni hybrid carbon dots:

[0078] 250-1050 mg of nickel sulfate hexahydrate, 300-1200 mg of glucose, 175-700 mg of polyethyleneimine, 150-612 mg of dithiodibenzoic acid, and 100-250 mg of 4-methoxypyridine were added to 50-300 mL of deionized water and stirred for 15-60 min. The pH was then adjusted to 9 with 0.5-2 mol / L sodium hydroxide solution. The mixture was stirred and reacted at 50-70°C for 2-8 h. The resulting precursor was transferred to a reactor and reacted at 230-250°C for 5-20 h. The mixture was centrifuged, washed, and vacuum dried to obtain Ni-hybridized carbon dots: Ni-CDs.

[0079] S2-3, partially oxidize Ti3C2T x MXene and Ni hybrid carbon dots self-assemble to obtain antibacterial wave-absorbing particles:

[0080] 0.75-3 g Ni hybrid carbon dots were added to 40-160 mL 0.5-2 mol / L hydrochloric acid, ultrasonically treated at 50-70 ° C for 0.5-2 h, filtered, and the solid product was washed with deionized water until neutral, then added to 25-100 mL deionized water and ultrasonically dispersed for 1-3 h to obtain a carbon dot dispersion; 0.5-2 g partially oxidized Ti3C2T x MXene was added to 25-100 mL of deionized water and ultrasonically dispersed for 1-4 h to obtain a MXene dispersion.

[0081] The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 500-2000 rpm for 5-20 hours, and then allowed to stand for 1-4 hours, filtered, washed, and freeze-dried to obtain antibacterial wave-absorbing particles.

[0082] In the present invention, the fiber body is prepared by a core-skin composite spinning process using PET polyester chips as the core material and a flame retardant and wave absorbing mixture as the skin material;

[0083] The antibacterial absorbing layer is obtained by coating the antibacterial absorbing particles on the surface of the fiber body through an impregnation process. The specific impregnation process is as follows:

[0084] The antibacterial absorbing particles are added to deionized water and ultrasonically dispersed for 1-4 hours to prepare an antibacterial absorbing particle dispersion with a concentration of 5-20 mg / mL; the fiber body is ultrasonically washed in deionized water for 0.5-2 hours, taken out and dried at 80-120°C for 1-4 hours, placed in the antibacterial absorbing particle dispersion, immersed at 50-70°C for 10-30 minutes, taken out and dried at 80-120°C for 1-4 hours to complete one immersion, and the immersion is repeated 2-8 times to form an antibacterial absorbing layer on the surface of the fiber body.

[0085] Invention mechanism:

[0086] 1. Overall Mechanism: The flame-retardant and antibacterial absorbing PET fiber prepared by the present invention has a multi-layer composite structure composed of a core layer, a flame-retardant and antibacterial absorbing barrier layer, and an antibacterial absorbing layer coated in sequence from the inside out. The core layer is the main structure of the PET fiber, and the flame-retardant and antibacterial absorbing barrier layers and the antibacterial absorbing layer are functional structural layers formed by sequential coating. The antibacterial absorbing layer can provide excellent electromagnetic wave absorption capabilities through the antibacterial absorbing particles therein, effectively protecting against electromagnetic pollution. It can also provide excellent antibacterial properties through the active oxygen generated under light and / or electromagnetic wave irradiation. In addition to improving the flame retardancy, the flame-retardant and antibacterial absorbing barrier layer can also provide excellent electromagnetic wave reflection and absorption capabilities through the flame-retardant and antibacterial absorbing particles therein. This allows the portion of the incident electromagnetic wave not absorbed by the antibacterial absorbing layer to be absorbed and reflected by the flame-retardant and antibacterial absorbing barrier layer, thereby enabling multiple reflections and absorption between the antibacterial and flame-retardant absorbing barrier layers, ultimately significantly improving the electromagnetic wave shielding capability and reducing the amount of electromagnetic wave transmission. Furthermore, the flame-retardant absorbing barrier layer, through its antibacterial absorbing particles, can also act as a barrier to reactive oxygen species generated within the antibacterial absorbing layer, preventing them from entering the core layer and causing aging and degradation of the polyester therein. Furthermore, the flame-retardant absorbing barrier layer improves the mechanical strength and antistatic properties of the fiber. The following further analyzes and explains the preparation and mechanism of action of the antibacterial absorbing particles in the antibacterial absorbing layer and the flame-retardant absorbing particles in the flame-retardant absorbing barrier layer.

[0087] 2. Preparation and mechanism of action of antibacterial wave-absorbing particles:

[0088] 2-1. Preparation mechanism:

[0089] First, Ti3C2T X MXene is calcined at high temperature in air atmosphere. By controlling the calcination temperature and time, its partial oxidation is achieved, and the Ti in it is oxidized to TiO2, and Ti3C2T3O2 loaded in situ is obtained. XMXene materials, the TiO2 obtained in this way can be evenly distributed on Ti3C2T X MXene has a lamellar structure with good dispersion and more uniform particle size;

[0090] Then, nickel oxide-doped carbon dots, namely Ni hybrid carbon dots, were synthesized via a hydrothermal method using nickel sulfate hexahydrate as the nickel source and glucose, polyethyleneimine, dithiodibenzoic acid, and 4-methoxypyridine as composite carbon sources.

[0091] Finally, Ni hybrid carbon dots were assembled onto partially oxidized Ti3C2T x On MXene, antibacterial wave-absorbing particles are obtained: Ni hybrid carbon dots are first immersed in hydrochloric acid under ultrasonic action, and a large amount of Ni is generated on the Ni hybrid carbon dots through the reaction between hydrochloric acid and nickel oxide. 2+ , and then Ni hybridized carbon dots were mixed with partially oxidized Ti3C2T x MXene is mixed in solution and partially oxidizes Ti3C2T x The negatively charged hydroxyl and fluoride ions contained in MXene interact with Ni 2+ electrostatic coupling, and partially oxidized Ti3C2T x The physical adsorption of the layered structure in MXene enables the Ni hybrid carbon dots to be connected and assembled to the partially oxidized Ti3C2T x The antibacterial and wave-absorbing particles were obtained by uniformly loading the MXene.

[0092] 2-2. Main mechanism of action:

[0093] Ti3C2T x MXene is a two-dimensional nanolayered material with a large specific surface area and a multilayer structure. It also has excellent electromagnetic shielding and wave absorption properties. The intrinsic electric polarization and dipole polarization caused by surface defects can efficiently dissipate electromagnetic wave energy (Zhang Hengyu. Research on MXene-based flexible and high-efficiency wave-absorbing textile materials [D]. Donghua University, 2024.).

[0094] In the present invention, Ti3C2T x MXene, as the matrix material of antibacterial absorbing particles, can provide excellent absorbing performance. xAfter TiO2 is in situ formed on MXene, on the one hand, TiO2 can not only optimize impedance matching, but also effectively prevent stacking and provide a heterogeneous interface, providing a conductive path for charge carriers, and further improving the wave absorption properties; on the other hand, TiO2 is an excellent photosensitive material that can generate electron-hole pairs under light. The electrons after the transition react with substrates (such as H2O, O) to produce reactive oxygen species, such as singlet oxygen (¹O2), superoxide radicals (O2⁻), hydroxyl radicals (OH·), etc. Reactive oxygen species have strong oxidizing properties and can destroy cell membranes, proteins and DNA structures, thereby exhibiting excellent antibacterial ability.

[0095] The Ni-hybridized carbon dots prepared in this invention exhibit unique wave absorption response properties, allowing them to efficiently generate reactive oxygen species after absorbing electromagnetic waves. This is due to the energy level transition of the electrons within the Ni-hybridized carbon dots, from a low-energy orbital to a high-energy orbital. The transitioned electrons react with oxygen molecules (O2) or water molecules (H2O) to generate singlet oxygen (¹O2), superoxide radicals (O2⁻), and hydroxyl radicals (OH·).

[0096] That is, Ni hybridized carbon dots can not only absorb electromagnetic waves, but also generate active oxygen with antibacterial ability under the action of electromagnetic waves, which is beneficial to the use of fibers. x The combination of MXene enables the antibacterial absorbing layer on the fiber surface prepared using it to produce active oxygen with antibacterial ability under light or electromagnetic wave irradiation, which can give the fiber excellent antibacterial and antibacterial properties.

[0097] The Ni doped in the carbon dots is nickel oxide nanoparticles uniformly hybridized with the carbon dots, synthesized during a high-temperature and high-pressure hydrothermal reaction. Nickel oxide nanoparticles can further improve the absorption performance. Its main mechanism of action includes: nickel oxide adjusts the electrical conductivity and dielectric constant of the composite material, reduces the reflection of electromagnetic waves on the surface of the material, improves the impedance matching characteristics, and allows more electromagnetic waves to enter the material and be consumed. The polar molecular structure of nickel oxide produces dipole polarization under an alternating electromagnetic field, which can consume electromagnetic energy (Wang Huiya. Preparation of biomass porous carbon / nickel oxide composite materials and research on their absorption properties [D]. Yunnan University, 2019.).

[0098] Partially oxidized Ti3C2T x MXene has a good loading capacity on Ni hybrid carbon dots, which can better achieve uniform distribution of Ni hybrid carbon dots and partially oxidize Ti3C2T x MXene can provide electron transport and improve the electron-hole separation efficiency, thereby enhancing the wave absorption performance of Ni-hybridized carbon dots and the catalytic ability to produce active oxygen under electromagnetic wave excitation.

[0099] 3. Preparation and action mechanism of flame retardant and wave absorbing mixture:

[0100] 3-1. Preparation mechanism:

[0101] First, the graphene oxide is oxidized with a mixture of H2O2 and nitric acid to enrich the carboxyl groups on its surface to obtain carboxylated graphene oxide;

[0102] Then, zinc oxide hybridized ferroferric oxide was in situ deposited on the carboxylated graphene oxide by a one-pot hydrothermal method to obtain composite absorbing particles; due to the abundant carboxyl groups on the surface, it can attract Fe 2+ 、Fe 3+ , Zn ions, thereby facilitating the deposition of zinc oxide hybridized ferroferric oxide on graphene oxide;

[0103] Finally, polyaniline was grafted onto the composite absorbing particles by in-situ polymerization to obtain flame-retardant absorbing particles.

[0104] 3-2, Mechanism of action:

[0105] Fe3O4 has high saturation magnetization, coercivity and resistivity, making it a commonly used magnetic loss-type absorbing material (Pan Hong, Hu Lei, Xu Lihui, et al. Green low-temperature preparation of Fe3O4 and its composite material absorption performance [J]. Materials Engineering, 2025, 53 (4): 150-162.). However, the loss mechanism of single-material absorbing materials is simple, the absorption efficiency is low, and it is difficult to meet the use requirements. In the present invention, by hybridizing ZnO in Fe3O4, the dielectric loss is increased through its polarization effect and interface polarization energy, thereby enhancing the absorption performance (Wang S, Li D, Zhou Y, et al. Hierarchical Ti3C2TxMXene / Ni Chain / ZnO Array Hybrid Nanostructures on Cotton Fabric for Durable Self-Cleaning and Enhanced Microwave Absorption [J]. ACS nano, 2020 (7): 14.). Furthermore, loading zinc oxide hybrid ferroferric oxide with carboxylated graphene oxide further enhances its absorption performance. This is primarily due to the excellent conductivity of graphene oxide itself, which achieves electromagnetic wave absorption through the synergistic effect of conductivity loss and polarization loss. Conductive materials reflect and guide electromagnetic waves, generating current and magnetic polarization opposite to the electromagnetic field within the conductive material, which reflects or absorbs some of the electromagnetic waves, reducing the amount of electromagnetic waves transmitted, thereby achieving shielding (Hao Xiuyang, Yun Gaojie. Types of Electromagnetic Radiation-Proof Textiles and Their Product Standards [J]. Textile Industry and Technology, 2013, 2:42-43).

[0106] On the other hand, graphene oxide has excellent mechanical properties and temperature resistance. When added to the flame-retardant and wave-absorbing barrier layer, it is also beneficial to improve the tensile strength and toughness of the fiber. Furthermore, graphene oxide can improve the barrier performance of the flame-retardant and wave-absorbing barrier layer against active oxygen, preventing active oxygen from entering the core layer and accelerating polymer aging, thereby damaging the main structure of the polyester fiber. The reason is that graphene oxide has a two-dimensional sheet structure, which can form a dense barrier, effectively extending the path for oxygen and corrosive media to penetrate the polymer, and reducing the penetration rate.

[0107] In this invention, grafting polyaniline onto the composite absorbing particles improves electrical conductivity, modulates dielectric properties, and optimizes electromagnetic wave reflection loss. The positive charges on the molecular chains trigger dipole interactions, forming polaron conductive pathways. This structural change significantly enhances the material's ability to attenuate electromagnetic waves. Furthermore, the grafting of polyaniline improves uniform dispersion within the flame-retardant, absorbing mixture. Furthermore, the enhanced conductivity improves the fiber's antistatic properties.

[0108] 4. The coordination mechanism of antibacterial absorbing layer and flame retardant absorbing barrier layer:

[0109] In the preparation process of the antibacterial absorbing layer, the combination of the two can facilitate the formation of the antibacterial absorbing layer: Ti3C2T in the antibacterial absorbing particles X The surface of MXene contains rich fluoride ions and hydroxyl groups, and the surface of the carbon dots in the antibacterial absorbing particles contains a large number of carboxyl groups and hydroxyl groups; the polyaniline chain segments in the flame retardant absorbing barrier layer contain a large amount of positively charged nitrogen, which enables the antibacterial absorbing particles to be assembled and coated on the surface of the flame retardant absorbing barrier layer through electrostatic coupling to form an antibacterial absorbing layer.

[0110] Cooperation in mechanism of action:

[0111] 1. The antibacterial absorbing layer provides antibacterial properties by generating reactive oxygen species under light and / or magnetic wave irradiation. These reactive oxygen species attack polymer chains, causing them to break and accelerating polymer aging. Therefore, if a large amount of reactive oxygen species enters the core layer, which forms the main structure of the PET fiber, it can accelerate aging of the PET fiber, impairing its mechanical properties and ultimately affecting the overall strength of the fiber. The present invention effectively overcomes this problem by incorporating a flame-retardant, absorbing barrier layer. The flame-retardant, absorbing barrier layer forms a physical barrier that effectively prevents reactive oxygen species from entering the core layer, thereby addressing the adverse effects of reactive oxygen species.

[0112] 2. The antibacterial absorbing layer has excellent absorbing performance. After the incident electromagnetic wave is absorbed by the antibacterial absorbing layer, the remaining part will be absorbed and reflected by the flame retardant absorbing barrier layer, and the reflected part will be absorbed or reflected by the antibacterial absorbing layer again. Therefore, through the cooperation of the antibacterial absorbing layer and the flame retardant absorbing barrier layer, multiple reflections and absorptions of electromagnetic waves can be achieved, which ultimately significantly improves the electromagnetic wave shielding ability of the fiber and reduces the amount of electromagnetic wave penetration.

[0113] The above is the overall concept of the present invention. Detailed examples and comparative examples are provided below to further illustrate the present invention.

[0114] Sources of the main raw materials in the examples and comparative examples are as follows:

[0115] Polyester chips (polyethylene terephthalate chips), model CB-602, relative viscosity 0.8 dl / g, acid value 35 mg KOH / g, Far Eastern Industries (Shanghai) Co., Ltd.; vacuum dried at 120°C for 6 h before use;

[0116] Ammonium polyphosphate, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0117] EEA (ethylene-ethyl acrylate copolymer), Arkema EEA 8200, France, purchased from Suzhou Guoyao New Materials Co., Ltd.;

[0118] Graphene oxide, model MG-NGO-01, single-layer diameter 50-500 nm, Shanghai Maoguo Nanotechnology Co., Ltd.

[0119] PVP (polyvinylpyrrolidone), Shanghai Hongzhuang Chemical Technology Co., Ltd.;

[0120] Aniline, Nanjing Furunda Chemical Co., Ltd.;

[0121] Ammonium persulfate, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0122] Polyethyleneimine, MW10000, Shanghai Youen Chemical Co., Ltd.;

[0123] Dithiodibenzoic acid, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0124] 4-Methoxypyridine, Shanghai Hongzhuang Chemical Technology Co., Ltd.

[0125] Example 1

[0126] A flame-retardant and antibacterial absorbing PET fiber comprises a fiber body and an antibacterial absorbing layer arranged on the surface of the fiber body. The fiber body is a skin-core composite structure, and comprises a core layer and a flame-retardant and absorbing barrier layer from the inside to the outside. The fiber body is prepared by a skin-core composite spinning process using PET polyester chips as the core layer raw material and a flame-retardant and absorbing mixture as the skin layer raw material. The antibacterial absorbing layer is obtained by coating the surface of the fiber body with antibacterial absorbing particles.

[0127] The preparation method of the flame-retardant and antibacterial absorbing PET fiber is specifically as follows:

[0128] Step 1: By weight, 100 parts of PET polyester chips, 13 parts of flame retardant, 28 parts of flame retardant and wave-absorbing particles, and 3 parts of compatibilizer were mixed at 70° C. and 500 rpm for 2 hours to obtain a flame retardant and wave-absorbing mixture;

[0129] Among them, the flame retardant is ammonium polyphosphate and the compatibilizer is EEA (ethylene-ethyl acrylate copolymer);

[0130] Step 2: Adding PET polyester chips as the core layer raw material and the flame retardant and microwave absorbing mixture as the skin layer raw material to their respective corresponding screw extruders for melt extrusion, and then adopting a skin-core composite spinning process to prepare a fiber body; the mass ratio of the skin layer raw material to the core layer raw material is 2:8;

[0131] The melt extrusion temperature of the core layer material is 275°C, and the melt extrusion temperature of the skin layer material is 280°C;

[0132] The process parameters of the core-skin composite spinning are as follows: spinning temperature 270°C, spinning speed 4000m / min, side blowing temperature 20°C, and side blowing speed 0.5m / s;

[0133] Step 3: Using the antibacterial absorbing particles to form an antibacterial absorbing layer on the surface of the fiber body by using an impregnation process:

[0134] Antibacterial absorbing particles were added to deionized water and ultrasonically dispersed for 2 hours to prepare an antibacterial absorbing particle dispersion with a concentration of 10 mg / mL; the fiber body was ultrasonically washed in deionized water for 1 hour, taken out and dried at 100°C for 2 hours, placed in the antibacterial absorbing particle dispersion, immersed at 55°C for 20 minutes, taken out and dried at 100°C for 2 hours to complete one immersion, and the immersion was repeated 4 times to form an antibacterial absorbing layer on the surface of the fiber body, and finally a flame-retardant and antibacterial absorbing PET fiber was obtained.

[0135] In this example, flame retardant wave absorbing particles are prepared by the following steps:

[0136] S1-1. Preparation of carboxylated graphene oxide:

[0137] 2 g of graphene oxide was added to a mixture of 50 mL of 20 wt% H2O2 and 100 mL of 60 wt% nitric acid, stirred and refluxed at 80 ° C for 6 h, filtered, washed with deionized water until neutral, and vacuum dried at 90 ° C for 12 h to obtain carboxylated graphene oxide;

[0138] S1-2, loading zinc oxide hybridized ferroferric oxide on carboxylated graphene oxide to obtain composite wave-absorbing particles:

[0139] 1 g of carboxylated graphene oxide and 4.5 g of urea were added to 100 mL of deionized water and ultrasonically dispersed for 1 hour to obtain a graphene dispersion. 1 g of PVP (polyvinyl pyrrolidone), 0.381 g of FeCl2, 0.972 g of FeCl3, and 0.322 g of ZnSO4 were added to 100 mL of a mixed solvent consisting of deionized water and ethylene glycol in a volume ratio of 1:1 and stirred for 15 minutes. The resulting mixture was added to the graphene dispersion under stirring and stirred for 1 hour. The resulting product was transferred to a reactor and reacted at 220°C for 12 hours. The product was cooled to room temperature and centrifuged. The solid product was washed with deionized water and dried in vacuo at 90°C for 24 hours to obtain composite absorbing particles.

[0140] S1-3, performing polyaniline hybridization treatment on the composite wave-absorbing particles to obtain flame-retardant wave-absorbing particles:

[0141] 0.2 g of composite absorbing particles were added to 100 mL of deionized water and ultrasonically dispersed for 45 min. 0.35 g of aniline was added and stirred for 1 h. 0.85 g of ammonium persulfate was added at 5 °C and the pH of the reaction system was adjusted to 2 with 30 wt% hydrochloric acid. The mixture was stirred at room temperature for 8 h and centrifuged. The solid product was washed with deionized water and vacuum dried at 80 °C for 24 h to obtain flame-retardant absorbing particles.

[0142] In this example, antibacterial wave-absorbing particles were prepared by the following steps:

[0143] S2-1. Preparation of partially oxidized Ti3C2T X MXene:

[0144] S2-1-1. Preparation of Ti3C2T X MXene:

[0145] Ti3C2T X MXene was prepared by conventional etching method: 1.35g LiF was added to 25mL 9M HCl solution and stirred for 30min to obtain etching solution; 2g Ti3AlC2 was added to the etching solution and stirred at 45℃ for 48h. After the reaction, the product was centrifuged and washed with deionized water until the supernatant pH was 6, and then dried in vacuum at 60℃ for 12h to obtain Ti3C2T X MXene;

[0146] S2-1-2, Partial oxidation treatment:

[0147] Ti3C2T X MXene was calcined at 350 °C for 3 h in air atmosphere, cooled to room temperature, and ground to obtain powdered partially oxidized Ti3C2T x MXene;

[0148] S2-2. Preparation of Ni hybrid carbon dots:

[0149] 524 mg of nickel sulfate hexahydrate, 600 mg of glucose, 350 mg of polyethyleneimine, 306 mg of dithiodibenzoic acid and 218 mg of 4-methoxypyridine were added to 150 mL of deionized water and stirred for 30 min. Then, the pH was adjusted to 9 with 1 mol / L sodium hydroxide and stirred at 60 ° C for 4 h. The resulting precursor was transferred to a reactor and reacted at 230 ° C for 10 h. After cooling to room temperature and centrifugation, the solid product was washed with ethanol and deionized water in sequence and dried in vacuo at 80 ° C for 12 h to obtain Ni hybrid carbon dots: Ni-CDs;

[0150] S2-3, partially oxidize Ti3C2T x Self-assembly of MXene and Ni hybrid carbon dots:

[0151] 1.5 g of Ni-hybridized carbon dots were added to 80 mL of 1 mol / L hydrochloric acid and ultrasonically treated at 60 °C for 1 h. The solid product was filtered and washed with deionized water until neutral. The solid product was then added to 50 mL of deionized water and ultrasonically dispersed for 1.5 h to obtain a carbon dot dispersion.

[0152] 1g partially oxidized Ti3C2T x MXene was added to 50 mL of deionized water and ultrasonically dispersed for 2 h to obtain a MXene dispersion;

[0153] The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 1000 rpm for 10 h. Then the mixture was allowed to stand for 2 h and filtered. The solid product was washed with deionized water and freeze-dried to obtain antibacterial absorbing particles.

[0154] Reference Figure 1 , is the infrared absorption spectrum of the flame retardant wave absorbing particles prepared in this embodiment, Figure 2 The infrared absorption spectra of the antibacterial wave-absorbing particles prepared in this example illustrate the successful preparation of the two particles.

[0155] Example 2

[0156] The only difference between this example and Example 1 is that:

[0157] Step 1 of this example is specifically as follows: by weight, 100 parts of PET polyester chips, 13 parts of flame retardant, 24 parts of flame retardant absorbing particles, and 3 parts of compatibilizer are mixed at 70° C. and 500 rpm for 2 hours to obtain a flame retardant absorbing mixture.

[0158] Example 3

[0159] The only difference between this example and Example 1 is that:

[0160] Steps S2-3 in this example are specifically as follows:

[0161] 1.2 g of Ni-hybridized carbon dots were added to 80 mL of 1 mol / L hydrochloric acid and ultrasonically treated at 60 °C for 1 h. The solid product was filtered and washed with deionized water until neutral. The solid product was then added to 50 mL of deionized water and ultrasonically dispersed for 1.5 h to obtain a carbon dot dispersion.

[0162] 1g partially oxidized Ti3C2T x MXene was added to 50 mL of deionized water and ultrasonically dispersed for 2 h to obtain a MXene dispersion;

[0163] The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 1000 rpm for 10 h. Then the mixture was allowed to stand for 2 h and filtered. The solid product was washed with deionized water and freeze-dried to obtain antibacterial absorbing particles.

[0164] Example 4

[0165] A flame-retardant and antibacterial absorbing PET fiber comprises a fiber body and an antibacterial absorbing layer arranged on the surface of the fiber body. The fiber body is a skin-core composite structure, and comprises a core layer and a flame-retardant and absorbing barrier layer from the inside to the outside. The fiber body is prepared by a skin-core composite spinning process using PET polyester chips as the core layer raw material and a flame-retardant and absorbing mixture as the skin layer raw material. The antibacterial absorbing layer is obtained by coating the surface of the fiber body with antibacterial absorbing particles.

[0166] The preparation method of the flame-retardant and antibacterial absorbing PET fiber is specifically as follows:

[0167] Step 1: By weight, 100 parts of PET polyester chips, 13 parts of flame retardant, 28 parts of flame retardant and wave-absorbing particles, and 3 parts of compatibilizer were mixed at 80° C. and 600 rpm for 1.5 hours to obtain a flame retardant and wave-absorbing mixture;

[0168] Among them, the flame retardant is ammonium polyphosphate and the compatibilizer is EEA (ethylene-ethyl acrylate copolymer);

[0169] Step 2: Adding PET polyester chips as the core layer raw material and the flame retardant and microwave absorbing mixture as the skin layer raw material to their respective corresponding screw extruders for melt extrusion, and then adopting a skin-core composite spinning process to prepare a fiber body; the mass ratio of the skin layer raw material to the core layer raw material is 2:8;

[0170] The melt extrusion temperature of the core layer material is 270°C, and the melt extrusion temperature of the skin layer material is 275°C;

[0171] The process parameters of the core-skin composite spinning are as follows: spinning temperature 270°C, spinning speed 4000m / min, side blowing temperature 20°C, and side blowing speed 0.5m / s;

[0172] Step 3: Using the antibacterial absorbing particles to form an antibacterial absorbing layer on the surface of the fiber body by using an impregnation process:

[0173] Antibacterial absorbing particles were added to deionized water and ultrasonically dispersed for 2 hours to prepare an antibacterial absorbing particle dispersion with a concentration of 10 mg / mL; the fiber body was ultrasonically washed in deionized water for 1 hour, taken out and dried at 90°C for 3 hours, placed in the antibacterial absorbing particle dispersion, immersed at 50°C for 20 minutes, taken out and dried at 90°C for 3 hours to complete one immersion, and the immersion was repeated 4 times to form an antibacterial absorbing layer on the surface of the fiber body, and finally a flame-retardant and antibacterial absorbing PET fiber was obtained.

[0174] The preparation method of the flame retardant wave-absorbing particles and the antibacterial wave-absorbing particles is the same as that in Example 1.

[0175] Comparative Example 1

[0176] A PET fiber has a core-skin composite structure, and comprises a core layer and a flame-retardant layer from the inside out. The fiber is prepared by a core-skin composite spinning process using PET polyester chips as the core layer raw material and a flame-retardant mixture as the skin layer raw material.

[0177] The preparation method of the PET fiber is specifically as follows:

[0178] Step 1: By weight, 100 parts of PET polyester chips, 13 parts of flame retardant, and 3 parts of compatibilizer were mixed at 70° C. and 500 rpm for 2 hours to obtain a flame retardant mixture;

[0179] Among them, the flame retardant is ammonium polyphosphate and the compatibilizer is EEA (ethylene-ethyl acrylate copolymer);

[0180] Step 2: Adding PET polyester chips as the core layer raw material and the flame retardant mixture as the skin layer raw material to their respective corresponding screw extruders for melt extrusion, and then adopting a skin-core composite spinning process to prepare a fiber body; the mass ratio of the skin layer raw material to the core layer raw material is 2:8;

[0181] The melt extrusion temperature of the core layer material is 275°C, and the melt extrusion temperature of the skin layer material is 280°C;

[0182] The process parameters of the core-skin composite spinning are as follows: spinning temperature 270°C, spinning speed 4000m / min, side blowing temperature 20°C, and side blowing speed 0.5m / s;

[0183] Comparative Example 2

[0184] The only difference between this example and Example 1 is that:

[0185] In the preparation step S1-2 of the flame-retardant and wave-absorbing particles of this example, no ZnSO4 is added.

[0186] Comparative Example 3

[0187] The only difference between this example and Example 1 is that:

[0188] In the preparation step S1-2 of the flame-retardant and wave-absorbing particles of this example, FeCl2 and FeCl3 are not added.

[0189] Comparative Example 4

[0190] The only difference between this example and Example 1 is that:

[0191] The antibacterial wave-absorbing particles of this example were prepared by the following steps:

[0192] S2-1. Preparation of Ti3C2T X MXene, the steps are the same as in Example 1;

[0193] S2-2, preparing Ni hybrid carbon dots, the steps are the same as those in Example 1;

[0194] S2-3, Ti3C2T x Self-assembly of MXene and Ni hybrid carbon dots:

[0195] 1.5 g of Ni-hybridized carbon dots were added to 80 mL of 1 mol / L hydrochloric acid and ultrasonically treated at 60 °C for 1 h. The solid product was filtered and washed with deionized water until neutral. The solid product was then added to 50 mL of deionized water and ultrasonically dispersed for 1.5 h to obtain a carbon dot dispersion.

[0196] 1gTi3C2T x MXene was added to 50 mL of deionized water and ultrasonically dispersed for 2 h to obtain a MXene dispersion;

[0197] The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 1000 rpm for 10 h. Then the mixture was allowed to stand for 2 h and filtered. The solid product was washed with deionized water and freeze-dried to obtain antibacterial absorbing particles.

[0198] Comparative Example 5

[0199] The only difference between this example and Example 1 is that:

[0200] In this example, the partially oxidized Ti3C2T prepared in Example 1 was used. X MXene as antibacterial wave-absorbing particles.

[0201] Comparative Example 6

[0202] The only difference between this example and Example 1 is that:

[0203] The antibacterial wave-absorbing particles of this example were prepared by the following steps:

[0204] S2-1. Preparation of partially oxidized Ti3C2T X MXene, the steps are the same as in Example 1;

[0205] S2-2, Preparation of Carbon Dots:

[0206] 600 mg of glucose, 350 mg of polyethyleneimine, 306 mg of dithiodibenzoic acid, and 218 mg of 4-methoxypyridine were added to 150 mL of deionized water and stirred for 30 min. The resulting precursor was transferred to a reactor and reacted at 230°C for 10 h. The mixture was cooled to room temperature and filtered through a 0.22 μm filter membrane. The filtrate was dialyzed in deionized water using a 1200 Da dialysis bag for 24 h. The dialyzate in the dialysis bag was freeze-dried to obtain carbon dots.

[0207] S2-3, partially oxidize Ti3C2T x Self-assembly of MXene and carbon dots:

[0208] 1.5 g of carbon dots were added to 80 mL of 1 mol / L hydrochloric acid and ultrasonically treated at 60°C for 1 h. The solid product was filtered and washed with deionized water until neutral. The solid product was then added to 50 mL of deionized water and ultrasonically dispersed for 1.5 h to obtain a carbon dot dispersion.

[0209] 1g partially oxidized Ti3C2T x MXene was added to 50 mL of deionized water and ultrasonically dispersed for 2 h to obtain a MXene dispersion;

[0210] The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 1000 rpm for 10 h. Then the mixture was allowed to stand for 2 h and filtered. The solid product was washed with deionized water and freeze-dried to obtain antibacterial absorbing particles.

[0211] Performance test case

[0212] 1. Electromagnetic shielding performance

[0213] The fibers are woven into 25×12×1.0 mm 3 After the rectangular sample was prepared, the electromagnetic shielding performance of the sample was tested in the frequency range of 8.2 to 12.4 GHz using an Agilent N5230A vector network analyzer. The test results are shown in Tables 1 and Figure 3 shown.

[0214] Table 1

[0215] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Total shielding effectiveness / dB 53 46 49 52 9 46 41 50 44 48

[0216] It can be seen from the test results that Examples 1-4 all have good electromagnetic shielding performance. The decrease in the content of flame-retardant absorbing particles in Example 2 leads to a decrease in electromagnetic shielding performance. The proportion of Ni hybridized carbon points in the antibacterial absorbing particles in Example 3 is reduced, which also reduces the electromagnetic shielding performance to a certain extent. The flame-retardant absorbing mixture in Comparative Example 1 does not contain flame-retardant absorbing particles, and the outer layer is not coated with an antibacterial absorbing layer, resulting in the largest decrease in electromagnetic shielding performance. The decrease in electromagnetic shielding performance in Comparative Example 2 shows that doping ZnO in the flame-retardant absorbing particles can improve the absorbing performance; the decrease in Comparative Example 3 is attributed to the fact that the flame-retardant absorbing particles do not contain ferroferric oxide; the results of Comparative Example 4 show that Ti3C2T x The titanium dioxide formed by partial oxidation treatment of MXene has an improved absorption performance; the antibacterial absorbing particles in comparative example 5 do not have Ni hybridized carbon dots, and the absorption performance is significantly reduced; the reason for the reduction in absorption performance in comparative example 6 is that nickel oxide is not hybridized in the carbon dots.

[0217] Further testing was conducted on the total shielding effectiveness reduction rate of Examples 1-4 after 500 washes. The test results are shown in Tables 2 and Figure 4 As shown:

[0218] Table 2

[0219] Example 1 Example 2 Example 3 Example 4 Total shielding effectiveness reduction rate / % 4.3 4.5 4.9 4.4

[0220] It can be seen that Examples 1-4 can still maintain relatively high electromagnetic shielding performance after water washing.

[0221] 2. Flame retardant properties

[0222] Refer to the GB / T 2406.2-2009 test, the test results are shown in Table 3 and Figure 5 As shown:

[0223] Table 3

[0224] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Limiting oxygen index (LOI) / % 37.5 34.1 36.4 37.3 21.7 35.7 36.9 37.3 36.6 37.2

[0225] The test results show that Examples 1-4 have good flame retardant properties.

[0226] 3. Antibacterial properties

[0227] According to GB / T 20944.3-2008 “Evaluation of antibacterial properties of textiles Part 3 Oscillation method”, the antibacterial rate of the prepared samples against Escherichia coli ATCC 25922 was determined by the oscillation flask method.

[0228] (1) Antibacterial performance test of antibacterial wave-absorbing particles:

[0229] The sample was the antibacterial wave-absorbing particles prepared in Example 1. Bacteria and antibacterial wave-absorbing particles were mixed and cultured. Different conditions were used for 15 minutes every hour. After 24 hours of culture, the antibacterial rate was measured and calculated. Based on the treatment conditions, four groups of experiments were included:

[0230] Group 1: light treatment alone;

[0231] Group 2: electromagnetic wave irradiation treatment alone;

[0232] Group 3: light treatment + electromagnetic wave irradiation treatment;

[0233] Group 4 (control group): no light exposure and no electromagnetic wave irradiation;

[0234] The illumination conditions were: fluorescent lamp (50W) for 30 minutes, cultured for 24 hours, and 30 cm away from the sample. The electromagnetic wave irradiation conditions were: 2000 MHz, 1W / m 2 , and the distance between it and the sample is 40 cm.

[0235] The test results are shown in Table 4 and Figure 6 As shown:

[0236] Table 4

[0237] Group 1 Group 2 Group 3 Group 4 Antibacterial rate / % 89.6 74.2 99.5 38.3

[0238] From the test results, it can be seen that compared with the control group, light or electromagnetic wave irradiation treatment can significantly improve the antibacterial rate, and the antibacterial rate of simultaneous light and electromagnetic wave irradiation treatment is the highest, indicating that both contribute to the antibacterial performance.

[0239] (2) Antibacterial performance test of fiber:

[0240] The samples were fibers prepared in Examples 1-4 and Comparative Examples 4-6. During the mixed culture process of the bacteria and the fiber samples, light treatment + electromagnetic wave irradiation treatment was applied every 1 hour (the light and electromagnetic wave irradiation conditions were the same as above), the treatment time was 15 minutes, and the antibacterial rate was detected and calculated after 24 hours of culture.

[0241] The test results are shown in Table 5 and Figure 7 :

[0242] Table 5

[0243] Example 1 Example 2 Example 3 Example 4 Comparative Example 4 Comparative Example 5 Comparative Example 6 Antibacterial rate / % 99.5 99.4 97.2 99.2 92.0 93.6 95.8

[0244] 4. Singlet oxygen generation performance

[0245] The sample was added to deionized water and ultrasonically dispersed in air for 45 min to prepare a dispersion with a concentration of 1 mg / mL. The singlet oxygen content generated after treatment for 30 min under different conditions was determined using a singlet oxygen fluorescent probe (SOSG, Shanghai Biyuntian Biotechnology Co., Ltd., model S0067).

[0246] SOSG is a probe that binds highly selectively to singlet oxygen. Before reacting with singlet oxygen, SOSG itself exhibits a faint blue fluorescence. After reaction with singlet oxygen, the resulting SOSG endoperoxide (SOSG-EP) emits green fluorescence with a maximum excitation wavelength of 504 nm and a maximum emission wavelength of 525 nm. Singlet oxygen production capacity is determined by measuring the intensity of the emission at 525 nm; greater emission intensity indicates greater singlet oxygen production capacity.

[0247] (1) The sample is the antibacterial wave-absorbing particles prepared in Example 1. The content of singlet oxygen generated after the dispersion is treated under different conditions for 30 minutes is measured, and the intensity of the emitted light at 525 nm is used to characterize it:

[0248] Group 1: light treatment alone;

[0249] Group 2: electromagnetic wave irradiation treatment alone;

[0250] Group 3: light treatment + electromagnetic wave irradiation treatment;

[0251] Group 4: no light exposure, no electromagnetic wave radiation;

[0252] The illumination conditions were: fluorescent lamp (50W) for 30 minutes, cultured for 24 hours, and 30 cm away from the sample. The electromagnetic wave irradiation conditions were: 2000 MHz, 1W / m 2 , and the distance between it and the sample is 40 cm.

[0253] The test results are shown in Table 6 and Figure 8 As shown:

[0254] Table 6

[0255] Group 1 Group 2 Group 3 Group 4 Fluorescence intensity (au) 8743 7255 9848 54

[0256] The test results show that singlet oxygen cannot be produced in the absence of light and electromagnetic wave irradiation (its fluorescence value is background fluorescence). The antibacterial absorbing particles can produce singlet oxygen under the application of light or electromagnetic wave irradiation alone. When light and electromagnetic wave irradiation are applied simultaneously, the singlet oxygen yield is the highest. The results combined with the antibacterial performance test show that the antibacterial performance comes from the generated ROS.

[0257] (2) The samples were the antibacterial wave-absorbing particles prepared in Examples 1-4 and Comparative Examples 4-6. The singlet oxygen content generated after the dispersion was treated under the same conditions (simultaneous application of light and electromagnetic wave irradiation, the light irradiation and electromagnetic wave irradiation conditions were the same as above) for 30 minutes was measured, and the intensity of the emitted light at 525 nm was used to characterize the content.

[0258] The test results are shown in Table 7 and Figure 9 As shown:

[0259] Table 7

[0260] Example 1 Example 2 Example 3 Example 4 Comparative Example 4 Comparative Example 5 Comparative Example 6 Fluorescence intensity (au) 9848 9831 9622 9812 9102 9259 9475

[0261] From the test results, it can be seen that Examples 1-4 can efficiently generate singlet oxygen, and the decrease in singlet oxygen yield in Comparative Example 4 is attributed to the x MXene was not partially oxidized, and the photogenerated singlet oxygen capability of titanium dioxide formed by partial oxidation was lost; the decreased singlet oxygen yield in Comparative Example 5 once again proved that Ni hybridized carbon dots were capable of generating singlet oxygen under electromagnetic wave irradiation; the results of Comparative Example 6 showed that Ni hybridization in carbon dots could improve the ability to generate singlet oxygen under electromagnetic wave irradiation.

[0262] 5. Breaking strength

[0263] The breaking strength of polyester fiber was measured with reference to the standard "GB / T 14344-2022 Test method for tensile properties of chemical fiber filaments". The test results are shown in Table 7 and Figure 10 As shown:

[0264] Table 7

[0265] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Breaking strength (cN / detx) 3.28 3.03 3.24 3.27 2.94 3.21 3.17 3.27 3.22 3.25

[0266] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A flame-retardant and antibacterial absorbing PET fiber, characterized in that: The fiber body comprises a fiber body and an antibacterial absorbing layer disposed on the surface of the fiber body. The fiber body is a skin-core composite structure, and comprises a core layer and a flame-retardant absorbing barrier layer from the inside out. The raw material of the flame-retardant absorbing barrier layer is a flame-retardant absorbing mixture, which comprises the following components by weight: 100 parts of PET polyester chips, 9-15 parts of flame retardant, 22-40 parts of flame-retardant absorbing particles, and 1.5-4 parts of compatibilizer. The flame retardant and wave absorbing particles are prepared by the following steps: S1-1, preparing carboxylated graphene oxide; S1-2, loading zinc oxide hybridized ferroferric oxide on carboxylated graphene oxide to obtain composite wave-absorbing particles; S1-3, performing polyaniline hybridization treatment on the composite wave-absorbing particles to obtain flame-retardant wave-absorbing particles; The antibacterial absorbing layer is obtained by coating the surface of the fiber body with antibacterial absorbing particles. The preparation method of the antibacterial absorbing particles includes the following steps: S2-1. Preparation of partially oxidized Ti3C2T X MXene; S2-2, preparation of Ni hybrid carbon dots; S2-3, partially oxidize Ti3C2T x MXene and Ni-hybridized carbon dots self-assemble to obtain antibacterial and wave-absorbing particles.

2. The flame-retardant and antibacterial absorbing PET fiber according to claim 1, characterized in that: The fiber body is made of PET polyester chips as the core material and flame retardant and wave absorbing mixture as the skin material through the skin-core composite spinning process; The antibacterial absorbing layer is obtained by coating the antibacterial absorbing particles on the surface of the fiber body through an impregnation process. The specific impregnation process is as follows: The antibacterial absorbing particles are dispersed in deionized water to obtain an antibacterial absorbing particle dispersion; the fiber body is ultrasonically washed in deionized water, taken out and dried, immersed in the antibacterial absorbing particle dispersion, taken out and dried, completing one immersion, and the immersion is repeated several times to form an antibacterial absorbing layer on the surface of the fiber body.

3. The flame-retardant and antibacterial absorbing PET fiber according to claim 2, characterized in that: The dipping process used to prepare the antibacterial absorbing layer is: The antibacterial absorbing particles are added to deionized water and ultrasonically dispersed for 1-4 hours to prepare an antibacterial absorbing particle dispersion with a concentration of 5-20 mg / mL; the fiber body is ultrasonically washed in deionized water for 0.5-2 hours, taken out and dried at 80-120°C for 1-4 hours, placed in the antibacterial absorbing particle dispersion, immersed at 50-70°C for 10-30 minutes, taken out and dried at 80-120°C for 1-4 hours to complete one immersion, and the immersion is repeated 2-8 times to form an antibacterial absorbing layer on the surface of the fiber body.

4. The flame-retardant and antibacterial wave-absorbing PET fiber according to claim 1, characterized in that: The flame retardant and wave absorbing particles are prepared by the following steps: S1-1, adding graphene oxide to a mixture of H2O2 and nitric acid, stirring and refluxing under heating, filtering, washing with deionized water until neutral, and drying to obtain carboxylated graphene oxide; S1-2. Carboxylated graphene oxide and urea are added to deionized water and ultrasonically dispersed to obtain a graphene dispersion; PVP, FeCl2, FeCl3, and ZnSO4 are added to a mixed solvent consisting of deionized water and ethylene glycol in a volume ratio of 1:1, and stirred. The resulting mixture is added to the graphene dispersion while stirring, and the resulting product is transferred to a reactor, reacted at 190-240° C. for 6-24 hours, centrifuged, washed, and vacuum dried to obtain composite absorbing particles; S1-3. Disperse the composite absorbing particles in deionized water, add aniline, stir, add ammonium persulfate, adjust the pH of the reaction system to 2-3, stir the reaction, centrifuge, wash, and vacuum dry to obtain flame-retardant absorbing particles.

5. The flame-retardant and antibacterial absorbing PET fiber according to claim 4, characterized in that: The flame retardant and wave absorbing particles are prepared by the following steps: S1-1. Take 2 g of graphene oxide and add it to a mixture of 50 mL of 20 wt% H2O2 and 100 mL of 60 wt% nitric acid. Stir and reflux at 80°C for 6 h. Filter, wash with deionized water until neutral, and dry to obtain carboxylated graphene oxide. S1-2, take 1g of carboxylated graphene oxide and 4.5g of urea, add them to 100mL of deionized water, and ultrasonically disperse them for 1h to obtain a graphene dispersion; add 1g of PVP, 0.381g of FeCl2, 0.972g of FeCl3, and 0.322g of ZnSO4 to 100mL of a mixed solvent consisting of deionized water and ethylene glycol in a volume ratio of 1:1, and stir for 15min. The resulting mixture is added to the graphene dispersion under stirring and stirred for 1h. The resulting product is transferred to a reactor, reacted at 220°C for 12h, centrifuged, washed, and vacuum dried to obtain composite absorbing particles; S1-3. 0.2 g of the composite absorbing particles was added to 100 mL of deionized water and ultrasonically dispersed for 45 min. 0.35 g of aniline was added and stirred for 1 h. 0.85 g of ammonium persulfate was added at 5° C. The pH of the reaction system was adjusted to 2 with 30 wt % hydrochloric acid. The mixture was stirred and reacted at room temperature for 8 h. The mixture was centrifuged, washed, and vacuum dried to obtain flame-retardant absorbing particles.

6. The flame-retardant and antibacterial absorbing PET fiber according to claim 1, characterized in that: The antibacterial wave-absorbing particles are prepared by the following steps: S2-1, Ti3C2T X MXene was calcined at 250-400 °C for 2-4 h in air atmosphere and ground to obtain partially oxidized Ti3C2T x MXene; S2-2, adding nickel sulfate hexahydrate, glucose, polyethyleneimine, dithiodibenzoic acid and 4-methoxypyridine to deionized water, stirring, adjusting the pH to 9, heating and stirring to react, transferring the resulting precursor to a reactor, reacting at 230-250° C. for 5-20 h, centrifuging, washing, and vacuum drying to obtain Ni hybrid carbon dots; S2-3, adding Ni hybrid carbon dots to hydrochloric acid, ultrasonicating, filtering, washing the solid product with deionized water until neutral, and then dispersing it in deionized water to obtain a carbon dot dispersion; partially oxidizing Ti3C2T x MXene is dispersed in deionized water to obtain a MXene dispersion; The carbon dot dispersion was added to the MXene dispersion under stirring, and the mixture was continuously stirred, allowed to stand, filtered, washed, and freeze-dried to obtain antibacterial and wave-absorbing particles.

7. The flame-retardant and antibacterial absorbing PET fiber according to claim 6, characterized in that: The antibacterial wave-absorbing particles are prepared by the following steps: S2-1, Ti3C2T X MXene was calcined at 350 °C for 3 h in air atmosphere and ground to obtain partially oxidized Ti3C2T x MXene; S2-2, 524 mg of nickel sulfate hexahydrate, 600 mg of glucose, 350 mg of polyethyleneimine, 306 mg of dithiodibenzoic acid, and 218 mg of 4-methoxypyridine were added to 150 mL of deionized water and stirred for 30 min. Then, the pH was adjusted to 9 with 1 mol / L sodium hydroxide solution, and the mixture was stirred and reacted at 60°C for 4 h. The resulting precursor was transferred to a reactor and reacted at 230°C for 10 h. The mixture was centrifuged, washed, and dried in vacuo to obtain Ni-hybridized carbon dots: Ni-CDs; S2-3, 1.5 g of Ni hybridized carbon dots were added to 80 mL of 1 mol / L hydrochloric acid, ultrasonically treated at 60°C for 1 h, filtered, and the solid product was washed with deionized water until neutral, then added to 50 mL of deionized water and ultrasonically dispersed for 1.5 h to obtain a carbon dot dispersion; 1g partially oxidized Ti3C2T x MXene was added to 50 mL of deionized water and ultrasonically dispersed for 2 h to obtain a MXene dispersion; The carbon dot dispersion was added to the MXene dispersion under stirring, and the stirring was continued at 1000 rpm for 10 h. Then, the mixture was allowed to stand for 2 h, filtered, washed, and freeze-dried to obtain antibacterial absorbing particles.

8. The flame-retardant and antibacterial wave-absorbing PET fiber according to claim 1, characterized in that: The compatibilizer is one or more of ethylene-ethyl acrylate, ethylene-vinyl acetate copolymer, and maleic anhydride grafted polyolefin elastomer; The flame retardant is one or more of ammonium polyphosphate, trihydroxyethyl phosphate, phenylphosphonic acid, and trihydroxymethylphosphine oxide.

9. A method for preparing the flame-retardant and antibacterial absorbing PET fiber according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Evenly mix PET polyester chips, flame retardant, flame retardant and wave-absorbing particles, and a compatibilizer to obtain a flame retardant and wave-absorbing mixture; Step 2: Adding PET polyester chips as the core layer material and the flame retardant and microwave absorbing mixture as the skin layer material to their respective corresponding screw extruders for melt extrusion, and then adopting a skin-core composite spinning process to prepare a fiber body; Step 3: The antibacterial and antibacterial absorbing particles are impregnated on the surface of the fiber body to form an antibacterial and antibacterial absorbing layer, thereby finally obtaining the flame-retardant and antibacterial absorbing PET fiber.

10. The method for preparing the flame-retardant and antibacterial wave-absorbing PET fiber according to claim 9, characterized in that: In step 2, the mass ratio of the skin layer raw material to the core layer raw material is 1:9~3.5:6.5; the melt extrusion temperature corresponding to the core layer raw material is 260-290°C, and the melt extrusion temperature corresponding to the skin layer raw material is 250-290°C; The spinning process parameters are: spinning temperature 260-280°C, spinning speed 2000-4500m / min, side blowing temperature 10-30°C, and side blowing speed 0.2-1m / s.

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