A multifunctional rare earth composite antibacterial fiber and its preparation method

Abstract

This invention provides a multifunctional rare-earth composite antibacterial fiber and its preparation method, comprising the following steps: 1. Mixing cerium salt and silicate ester compounds uniformly, adding solvent and urea, introducing N2 for protection, adding a pore-forming agent, and reacting to obtain a sol; 2. Quenching the sol with liquid nitrogen and freeze-drying; 3. Calcining and milling the gel under an inert atmosphere; 4. Adding rare-earth composite antibacterial additives to polyester particles, mixing uniformly, and extruding; 5. Mixing, melting, and spinning the rare-earth composite antibacterial polyester masterbatch with polyester chips to obtain the final product. The multifunctional composite antibacterial fiber of this invention can effectively block the aggregation phenomenon of Ce during oxide formation, thereby obtaining a material with superior performance; the abundant mobile oxygen vacancies of CeO2 nanoparticles form heterojunctions with silica, improving the ROS oxidation mechanism and promoting antibacterial performance.

Description

Technical Field

[0001] This invention belongs to the field of textiles, and in particular relates to a multifunctional rare earth composite antibacterial fiber and its preparation method. Background Technology

[0002] Viruses in the environment, as pathogenic microorganisms, infect humans through various routes, posing a serious threat to public health. For example, the SARS-CoV-2 (COVID-19) virus is easily transmitted through droplets or aerosols, then adheres to surfaces and is subsequently touched by the recipient. Fabrics are now used in a wide range of applications and uses. However, most antiviral fabrics have not yet been industrialized, and there is a lack of systematic research on antiviral fabrics. Therefore, due to the requirements for hygienic and clean fabrics, there is currently a large demand for antiviral textile fabrics. Medicine, health, and hygiene are important and growing sectors of the textile industry. Development is taking place due to the synchronous growth and advancement of technologies in the textile and medical fields. Furthermore, antiviral agents impart antiviral properties to treated fabrics by killing viruses on the fabric surface or preventing biofilm formation, thereby reducing the risk of infection and reinfection. Furthermore, since antiviral fabrics are reusable, they help reduce contamination, and the interaction methods can be categorized as: connecting viruses and preventing viral attachment and penetration into cells; generating highly reactive oxygen species and other ions and free radicals that adhere to the cell wall (spikes or membrane), disrupting the structure and function of viral proteins and nucleic acids, mimicking the cell nucleus to increase the host cell's immune response, and inhibiting viral budding and spread.

[0003] CeO2 nanoparticles have gained global appeal due to their unique and tunable properties, such as chemical stability, excellent catalytic activity, abundant availability of mobile oxygen vacancies, wide bandgap energy (3.2 eV), and superior optical properties. Furthermore, the exceptional oxygen storage capacity of CeO2 nanoparticles is a key control factor for various applications, particularly in catalysis. This superior oxygen generation and storage capacity of CeO2 is due to the higher content of surface oxygen vacancies compared to its bulk counterparts. In addition, Ce... 3+ and Ce 4+ The coexistence of multiple oxidation states is associated with redox reactions, which is crucial for adjusting their structural properties. Summary of the Invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and propose a multifunctional rare earth composite antibacterial fiber and its preparation method.

[0005] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0006] This invention provides a method for preparing multifunctional rare earth composite antibacterial fibers, comprising the following steps:

[0007] Step 1 involves mixing cerium salt and silicate ester compounds evenly, adding solvent, performing ultrasonic-microwave treatment, then adding urea to adjust the pH of the solution to 8-9, introducing N2 for protection, adding a pore-forming agent, and reacting to obtain a sol.

[0008] Step 2 involves quenching the sol with liquid nitrogen, freeze-drying, and then drying it to obtain a gel.

[0009] Step 3 involves calcining and milling the gel under an inert atmosphere to obtain a rare earth composite antibacterial additive.

[0010] Step 4 involves adding the rare earth composite antibacterial additive to the polyester particles, mixing them evenly, and extruding them to obtain rare earth composite antibacterial polyester masterbatch.

[0011] Step 5 involves mixing, melting, and spinning the aforementioned rare-earth composite antibacterial polyester masterbatch with polyester chips to obtain the multifunctional rare-earth composite antibacterial fiber. Step 1 utilizes ultrasonic-microwave synergistic treatment to promote homogeneous mixing at the molecular level, and uses urea-released NH3 to regulate pH, achieving uniform co-precipitation of the Ce-Si precursor. A pore-forming agent is added to induce the formation of a three-dimensional network structure in the sol. Step 2 involves vacuum freeze-drying the sol to retain the mesoporous structure, followed by gradient cross-linking in a constant-temperature oven to promote gel network densification.

[0012] Furthermore, in step 1, the solid-liquid ratio of cerium salt, silicate compound, solvent, urea and pore-forming agent is 6-15g:10-15g:150-200mL:5-12g:1-5mL.

[0013] Further, the cerium salt in step 1 is at least one of CeF4•3H2O, CeCl3•6H2O, CeBr2•7H2O, Ce(NO3)3•6H2O, or Ce2(SO4)3•4H2O; the silicate ester compound in step 1 is at least one of tetraethyl orthosilicate, tetramethyl orthosilicate, or tetrabutyl orthosilicate; the pore-forming agent in step 1 is polyethylene glycol; and the solvent in step 1 is methanol or ethanol.

[0014] Furthermore, in step 1, the ultrasonic power of the ultrasonic-microwave step is 300-450W, and the microwave temperature is 50-70℃.

[0015] Furthermore, the temperature of the freeze-drying step in step 2 is -40°C to -50°C; the temperature of the drying step in step 2 is 10-50°C.

[0016] Furthermore, the calcination step in step 3 is specifically as follows: the temperature of the first stage is 200-350℃, the time is 1-2 hours, the temperature of the second stage is 500-700℃, the time is 2-4 hours, and the heating rate is 5-10℃ / min; the inert atmosphere in step 3 is argon; the temperature of the sand milling step in step 3 is 20-30℃, the time is 4-6 hours, and the rotation speed is 2600-3800 rpm.

[0017] Furthermore, the mass ratio of the rare earth composite antibacterial additive to the polyester particles in step 4 is 1-3:100; the temperature of the extrusion step in step 4 is 220-260℃.

[0018] Furthermore, in step 5, the mass ratio of rare earth composite antibacterial polyester masterbatch to polyester chips is 1-3:10.

[0019] Furthermore, in step 5, the cavity temperature of the spinning step is 220-270℃, and the rotation speed is 2300-2500rpm.

[0020] The present invention also provides a multifunctional rare earth composite antibacterial fiber prepared by the preparation method described above.

[0021] Ce forms a stable three-dimensional network structure in tetraethyl orthosilicate through hydrolysis in alcohol and ultrasonic / microwave treatment. The addition of polyethylene glycol promotes the formation of a porous structure. The structure is stabilized by freeze-drying, followed by segmental calcination at high temperature to form a stable, open-pore structure. Rare earth cerium ions are encapsulated within the Si-O bonds, thus preventing the aggregation of Ce during oxide formation. Furthermore, the high-temperature calcination process causes ammonium bicarbonate to decompose into ammonia and carbon dioxide, resulting in numerous pores on the material surface due to gas depletion. This increases the specific surface area and expands the active sites, leading to improved material performance.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] The multifunctional composite antibacterial fiber of the present invention is prepared by two unique preparation methods: sol-gel method and bubble removal method. These methods can effectively block the aggregation phenomenon of Ce during the formation of oxides, thereby obtaining a material with better performance. The abundant mobile oxygen vacancies of CeO2 nanoparticles form heterojunctions with silicon dioxide, which improves the ROS oxidation mechanism and promotes antibacterial performance. Attached Figure Description

[0024] Figure 1 This is a scanning electron microscope image of the rare earth composite antibacterial additive described in the embodiments of the present invention;

[0025] Figure 2This is an image of an antibacterial agar plate as described in an embodiment of the present invention;

[0026] Figure 3 This is a bar chart illustrating the antibacterial rate as described in the embodiments of the present invention;

[0027] Figure 4 This is a physical image of the multifunctional rare earth composite antibacterial fiber described in an embodiment of the present invention. Detailed Implementation

[0028] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0029] Tetraethyl orthosilicate (TEOS); Tetramethyl orthosilicate (TMOS); Tetrabutyl orthosilicate (TPOS).

[0030] TMOS, TEOS, TPOS, sodium dodecylbenzenesulfonate, anhydrous ethanol, PBT powder, and PET powder were purchased from Beijing Chemical Plant (Beijing, China). CeF4•3H2O, CeCl3•6H2O, CeBr2•7H2O, and Ce2(SO4)3•4H2O were purchased from Maclean's Reagents Ltd. All chemicals were used without further treatment. Distilled water (ρ=18.2 MΩ•cm, 25℃) was from the Millipore Milli-Q water purification system.

[0031] The present invention will be described in detail below with reference to the embodiments.

[0032] Example 1

[0033] A method for preparing a multifunctional rare earth composite antibacterial fiber includes the following steps:

[0034] Step 1 involves mixing 10g Ce(NO3)3•6H2O with 12g tetraethyl orthosilicate until homogeneous, adding 180mL of ethanol, transferring the mixture into an ultrasonic-microwave reactor, adjusting the ultrasonic power to 400W and the temperature to 60℃ for ultrasonic-microwave treatment, then adding 10g of urea, adjusting the pH of the solution to 9, and introducing N2 for protection. Finally, 5mL of polyethylene glycol is added, and the reaction yields a sol.

[0035] Step 2 involves quenching the sol with liquid nitrogen, freeze-drying (-50℃, 12h), and drying at 25℃ to obtain a gel.

[0036] Step 3 involves calcining the gel in an inert atmosphere at 300°C for 1.5 hours, followed by calcination at 600°C for 3 hours. The calcination heating rate is 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration at 25%. The powder is then added to a sand mill at a temperature of 25°C, a speed of 3200 rpm, and a milling time of 5 hours to obtain a rare earth composite antibacterial additive.

[0037] Step 4 involves adding 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester granules, mixing them evenly so that the additive adheres evenly to the polyester granules, and then placing the mixed polyester granules in an oven to dry at 80°C. After extrusion at 250°C, rare earth composite antibacterial polyester masterbatch is obtained.

[0038] Step 5 involves mixing, melting, and spinning 10 parts of rare earth composite antibacterial polyester masterbatch with 100 parts of polyester chips (temperature 260℃, rotation speed 2400rpm) to obtain the multifunctional rare earth composite antibacterial fiber.

[0039] Comparative Example 1

[0040] A method for preparing a multifunctional rare earth composite antibacterial fiber includes the following steps:

[0041] Step 1 involves mixing 10g of Y(NO3)3•6H2O with 12g of tetraethyl orthosilicate, adding 180mL of ethanol, transferring the mixture into an ultrasonic-microwave reactor, adjusting the ultrasonic power to 400W and the temperature to 60℃ for ultrasonic-microwave treatment, then adding 10g of urea, adjusting the pH of the solution to 9, and introducing N2 for protection. Finally, 5mL of polyethylene glycol is added, and the reaction yields a sol.

[0042] Step 2 involves quenching the sol with liquid nitrogen, freeze-drying (-50℃, 12h), and drying at 25℃ to obtain a gel.

[0043] Step 3 involves calcining the gel in an inert atmosphere at 300°C for 1.5 hours, followed by calcination at 600°C for 3 hours. The calcination heating rate is 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration at 25%. The powder is then added to a sand mill at a temperature of 25°C, a speed of 3200 rpm, and a milling time of 5 hours to obtain a rare earth composite antibacterial additive.

[0044] Step 4 involves adding 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester granules, mixing them evenly so that the additive adheres evenly to the polyester granules, and then placing the mixed polyester granules in an oven to dry at 80°C. After extrusion at 250°C, rare earth composite antibacterial polyester masterbatch is obtained.

[0045] Step 5 involves mixing, melting, and spinning 10 parts of rare earth composite antibacterial polyester masterbatch with 100 parts of polyester chips (temperature 260℃, rotation speed 2400rpm) to obtain the multifunctional rare earth composite antibacterial fiber.

[0046] Comparative Example 2

[0047] A method for preparing a multifunctional rare earth composite antibacterial fiber includes the following steps:

[0048] Step 1 involves mixing 10g Ce(NO3)3•6H2O with 12g tetraethyl orthosilicate until homogeneous, adding 180mL of ethanol, transferring the mixture into an ultrasonic-microwave reactor, adjusting the ultrasonic power to 400W and the temperature to 60℃ for ultrasonic-microwave treatment, then adding 10g of urea, adjusting the pH of the solution to 9, and introducing N2 for protection. After the reaction, a sol is obtained.

[0049] Step 2 involves quenching the sol with liquid nitrogen, freeze-drying (-50℃, 12h), and drying at 25℃ to obtain a gel.

[0050] Step 3 involves calcining the gel in an inert atmosphere at 300°C for 1.5 hours, followed by calcination at 600°C for 3 hours. The calcination heating rate is 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration at 25%. The powder is then added to a sand mill at a temperature of 25°C, a speed of 3200 rpm, and a milling time of 5 hours to obtain a rare earth composite antibacterial additive.

[0051] Step 4 involves adding 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester granules, mixing them evenly so that the additive adheres evenly to the polyester granules, and then placing the mixed polyester granules in an oven to dry at 80°C. After extrusion at 250°C, rare earth composite antibacterial polyester masterbatch is obtained.

[0052] Step 5 involves mixing, melting, and spinning 10 parts of rare earth composite antibacterial polyester masterbatch with 100 parts of polyester chips (temperature 260℃, rotation speed 2400rpm) to obtain the multifunctional rare earth composite antibacterial fiber.

[0053] Comparative Example 3

[0054] A method for preparing a multifunctional rare earth composite antibacterial fiber includes the following steps:

[0055] Step 1 involves mixing 10g Ce(NO3)3•6H2O with 12g fumed silica until homogeneous, adding 180mL of ethanol, transferring the mixture into an ultrasonic-microwave reactor, adjusting the ultrasonic power to 400W and the temperature to 60℃ for ultrasonic-microwave treatment, then adding 10g of urea, adjusting the pH of the solution to 9, and introducing N2 for protection. Finally, 5mL of polyethylene glycol is added, and the mixture is reacted to obtain a mixed powder.

[0056] Step 2 involves subjecting the mixed powder to liquid nitrogen quenching, freeze drying (-50℃, 12h), and drying at 25℃ to obtain the powder.

[0057] Step 3 involves calcining the gel in an inert atmosphere at 300°C for 1.5 hours, followed by calcination at 600°C for 3 hours. The calcination heating rate is 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration at 25%. The powder is then added to a sand mill at a temperature of 25°C, a speed of 3200 rpm, and a milling time of 5 hours to obtain a rare earth composite antibacterial additive.

[0058] Step 4 involves adding 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester granules, mixing them evenly so that the additive adheres evenly to the polyester granules, and then placing the mixed polyester granules in an oven to dry at 80°C. After extrusion at 250°C, rare earth composite antibacterial polyester masterbatch is obtained.

[0059] Step 5 involves mixing, melting, and spinning 10 parts of rare earth composite antibacterial polyester masterbatch with 100 parts of polyester chips (temperature 260℃, rotation speed 2400rpm) to obtain the multifunctional rare earth composite antibacterial fiber.

[0060] like Figure 1As shown in the SEM image, a large number of uniformly distributed pores are visible on the material surface. The formation of these pores is attributed to the bubble template method, which creates a rich porous structure both inside and on the surface of the material. This porous structure significantly increases the specific surface area of ​​the material, providing a larger contact area for the reaction during the antibacterial process, facilitating sufficient contact between rare earth cerium ions and microorganisms, thereby enhancing antibacterial performance. Observation of the size and distribution of the pores reveals a relatively uniform characteristic. This indicates that the reaction and phase separation processes between the components are effectively controlled during the preparation process combining the sol-gel method and the bubble template method, allowing the bubble template inside the material to be uniformly dispersed, avoiding the potential performance inhomogeneity caused by excessively large or small local pores. Silica serves as the matrix of the material, and as can be seen from the image, it forms a continuous network structure. This network structure provides mechanical stability and support for the material, while also providing a basis for the loading and dispersion of cerium ions. The interaction between the silica network and cerium ions helps improve the antibacterial durability of the material because silica can protect cerium ions from the influence of the external environment, preventing their rapid loss or deactivation.

[0061] like Figure 2 and Figure 3 As shown, the antibacterial effect was poor when yttrium salts were used instead, because the Ce in yttrium nitrate... 3+ / Ce 4+ Reversible conversion effectively promotes free radical generation, endowing materials with higher reactivity. Other rare earth salts, lacking this valence change mechanism, struggle to maintain the same level of free radical catalytic efficiency. Furthermore, without the addition of the pore-forming agent polyethylene glycol, the system lacks a gas template, resulting in a porous structure, reduced specific surface area, fewer reaction sites, and consequently lower reactivity. A strategy employing controlled hydrolysis of silicate compounds in an alcohol medium is employed: a sol-gel process achieves uniform assembly of silicon-oxygen bonds within the organic chain, followed by high-temperature calcination to form nanoscale silica particles. These particles not only act as nucleation sites promoting micropore formation but also construct interconnected hierarchical pore structures through spatial cross-linking, significantly enhancing the material's specific surface area and surface reactivity, ultimately achieving a synergistic enhancement of antibacterial properties. Fumed silica cannot achieve the same results.

[0062] The white long fibrous fibers prepared by this invention (such as...) Figure 4 (As shown) Compared to commercially available brass fibers, it has the advantage of more convenient post-dyeing.

[0063] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a multifunctional rare earth composite antibacterial fiber, characterized in that: Includes the following steps: Step 1 involves mixing cerium salt and silicate ester compounds evenly, adding solvent, performing ultrasonic-microwave treatment, then adding urea to adjust the pH of the solution to 8-9, introducing N2 for protection, adding a pore-forming agent, and reacting to obtain a sol. Step 2 involves quenching the sol with liquid nitrogen, freeze-drying, and then drying it to obtain a gel. Step 3 involves calcining and milling the gel under an inert atmosphere to obtain a rare earth composite antibacterial additive. Step 4 involves adding the rare earth composite antibacterial additive to the polyester particles, mixing them evenly, and extruding them to obtain rare earth composite antibacterial polyester masterbatch. Step 5 involves mixing, melting, and spinning the rare earth composite antibacterial polyester masterbatch with polyester chips to obtain the multifunctional rare earth composite antibacterial fiber. In step 1, the solid-liquid ratio of cerium salt, silicate compound, solvent, urea and pore-forming agent is 6-15g: 10-15g: 150-200mL: 5-12g: 1-5mL; The ultrasonic power in the ultrasonic-microwave step of step 1 is 300-450W, and the microwave temperature is 50-70℃. The calcination step in step 3 is specifically as follows: the first stage temperature is 200-350℃, the time is 1-2 hours, the second stage temperature is 500-700℃, the time is 2-4 hours, and the heating rate is 5-10℃ / min; the inert atmosphere in step 3 is argon; the sand milling step in step 3 is at a temperature of 20-30℃, a time of 4-6 hours, and a rotation speed of 2600-3800 rpm. The cerium salt in step 1 is at least one of CeF4•3H2O, CeCl3•6H2O, CeBr2•7H2O, Ce(NO3)3•6H2O, or Ce2(SO4)3•4H2O; the silicate ester compound in step 1 is at least one of tetraethyl orthosilicate, tetramethyl orthosilicate, or tetrabutyl orthosilicate; the pore-forming agent in step 1 is polyethylene glycol; and the solvent in step 1 is methanol or ethanol. The temperature of the freeze-drying step in step 2 is -40℃ to -50℃; the temperature of the drying step in step 2 is 10-50℃.

2. The method for preparing multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: The mass ratio of rare earth composite antibacterial additive to polyester particles in step 4 is 1-3:100; the temperature of the extrusion step in step 4 is 220-260℃.

3. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: In step 5, the mass ratio of rare earth composite antibacterial polyester masterbatch to polyester chips is 1-3:

10.

4. The preparation method of the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: The chamber temperature in step 5, the spinning step, is 220-270℃, and the rotation speed is 2300-2500rpm.

5. A multifunctional rare earth composite antibacterial fiber prepared by the preparation method according to any one of claims 1-4.

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