Multifunctional rare earth composite antibacterial fiber and preparation method thereof

Abstract

The invention provides a multifunctional rare earth composite antibacterial fiber and a preparation method thereof, and the preparation method comprises the following steps: 1, uniformly mixing cerium salt and a silicate ester compound, adding a solvent and urea into the mixture, introducing N2 for protection, adding a pore-forming agent into the mixture, and reacting to obtain sol; 2, carrying out liquid nitrogen quenching and freeze drying on the sol; 3, calcining and sanding the gel in an inert atmosphere; 4, adding the rare earth composite antibacterial additive into the polyester particles, uniformly mixing, and extruding; and 5, mixing the rare-earth composite antibacterial polyester master batch with the polyester chips, melting, and spinning to obtain the rare-earth composite antibacterial polyester. The multifunctional composite antibacterial fiber provided by the invention can effectively block the agglomeration phenomenon of Ce in the process of forming an oxide, so that a material with better performance is obtained; rich mobile oxygen vacancies of CeO2 nanoparticles and silicon dioxide form heterojunctions, the ROS oxidation mechanism is improved, and the antibacterial performance is promoted.

Description

Technical Field

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

[0002] Viruses in the environment, as pathogens, infect humans through various pathways, posing a serious threat to public health. For example, the SARS-CoV2 (COVID-19) virus is easily transmitted through droplets or aerosols, then attaches to surfaces and subsequently comes into contact with the recipient. Fabrics are currently used in a wide range of applications and for a wide range of purposes. However, most antiviral fabrics have not yet been industrialized, and there is no systematic research on antiviral fabrics. Therefore, due to the demand for hygienic and clean fabrics, antiviral textiles are currently in high demand. Medicine, health, and hygiene are important and growing sectors in the textile industry. Developments are occurring due to the simultaneous growth and advancement of technology in the textile and pharmaceutical 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. In addition, since antiviral fabrics are reusable, they help reduce contamination, and the interaction methods can be divided into: connecting to viruses and preventing viruses from attaching and penetrating into cells; generating highly reactive oxygen species and other ions and free radicals that adhere to the wall (spikes or membranes), destroying the structure and function of viral proteins and nucleic acids, simulating the cell nucleus to increase the host cell's immune response, and inhibiting the budding and spread of the virus.

[0003] CeO2 nanoparticles have gained global appeal due to their unique and tunable properties, such as chemical stability, excellent catalytic activity, availability of abundant mobile oxygen vacancies, wide bandgap energy (3.2 eV), and improved optical properties. In addition, the extraordinary oxygen storage capacity of CeO2 nanoparticles is a key controlling factor in various applications, especially in catalysis. This exceptional oxygen storage capacity of CeO2 is due to the higher content of surface oxygen vacancies than its bulk counterpart. In addition, Ce 3+ and Ce 4+ The coexistence of multiple oxidation states of α-HBr is associated with redox reactions, which is crucial for tuning 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 proposes a multifunctional rare earth composite antibacterial fiber and a preparation method thereof.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows: The present invention provides a method for preparing a multifunctional rare earth composite antibacterial fiber, comprising the following steps: Step 1 is to mix the cerium salt and the silicate compound uniformly, add a solvent thereto, perform ultrasonic-microwave treatment, then add urea thereto, adjust the pH value of the solution to 8-9, introduce N2 protection, add a pore-forming agent thereto, and obtain a sol after reaction; Step 2 is to quench the sol with liquid nitrogen, freeze-dry, and dry it to obtain a gel; Step 3 is to calcine and sand-mill the gel under an inert atmosphere to obtain a rare earth composite antibacterial additive; Step 4 is adding the rare earth composite antibacterial additive to the polyester particles, mixing them evenly, and extruding to obtain a rare earth composite antibacterial polyester masterbatch; Step 5 involves mixing, melting, and spinning the rare earth composite antimicrobial polyester masterbatch with polyester chips to produce the multifunctional rare earth composite antimicrobial fiber. Step 1 involves promoting molecular-level homogeneous mixing through ultrasonic-microwave synergistic treatment. Urea is used to slowly release NH3 to regulate pH, achieving uniform coprecipitation of Ce-Si precursors. A pore-forming agent is then added to induce the sol to form a three-dimensional network structure. Step 2 involves vacuum freeze-drying the sol to retain the mesoporous structure, followed by gradient crosslinking in a constant temperature oven to promote densification of the gel network.

[0006] Furthermore, the solid-to-liquid ratio of the cerium salt, silicate compound, solvent, urea and pore-forming agent in step 1 is 6-15 g: 10-15 g: 150-200 mL: 5-12 g: 1-5 mL.

[0007] Furthermore, 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 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.

[0008] Furthermore, the ultrasonic power of the ultrasonic-microwave step in step 1 is 300-450W, and the microwave temperature is 50-70°C.

[0009] 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.

[0010] Furthermore, the calcination step in step 3 is specifically as follows: the temperature of the first section is 200-350°C, the time is 1-2 hours, the temperature of the second section is 500-700°C, the time is 2-4 hours, and the heating rate is 5-10°C / min; the inert atmosphere in step 3 is argon; the temperature of the sand grinding step in step 3 is 20-30°C, the time is 4-6 hours, and the rotation speed is 2600-3800 rpm.

[0011] Furthermore, the mass ratio of the rare earth composite antibacterial additive to the polyester particles in step 4 is 1-3:100; and the temperature of the extrusion step in step 4 is 220-260°C.

[0012] Furthermore, the mass ratio of the rare earth composite antibacterial polyester masterbatch to the polyester chips in step 5 is 1-3:10.

[0013] Furthermore, the cavity temperature of the spinning step in step 5 is 220-270° C., and the rotation speed is 2300-2500 rpm.

[0014] The present invention also provides a multifunctional rare earth composite antibacterial fiber prepared by the preparation method.

[0015] Through the hydrolysis of tetraethyl orthosilicate in alcohol and under an ultrasonic microwave environment, Ce forms a stable three-dimensional network structure in the ethyl silicate. The addition of polyethylene glycol promotes the formation of a porous structure. The structure is stabilized by freeze-drying, and then calcined in stages at high temperatures to form a stable porous structure. The rare earth cerium ions are encapsulated in the Si-O bond molecules, thereby preventing Ce from agglomerating during the oxide formation process. In addition, during the high-temperature calcination process, ammonium bicarbonate is thermally decomposed into ammonia and carbon dioxide, resulting in the appearance of numerous pores on the material surface caused by exhaust gas. This also increases the specific surface area of the material itself, expands the active sites, and improves the material's performance.

[0016] Compared with the prior art, the present invention has the following advantages: The multifunctional composite antibacterial fiber described in the present invention is prepared by two unique preparation methods: the sol-gel method and the bubble expulsion method. It can effectively block the agglomeration of Ce during the formation of oxides, thereby obtaining a material with better performance. The abundant mobile oxygen vacancies in CeO2 nanoparticles form heterojunctions with silica, improving the ROS oxidation mechanism and promoting antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a scanning electron microscope image of the rare earth composite antibacterial additive described in an embodiment of the present invention; Figure 2 This is the antibacterial agar plate image described in the embodiment of the present invention; Figure 3 This is a histogram of the antibacterial rate according to an embodiment of the present invention; Figure 4 This is a physical picture of the multifunctional rare earth composite antibacterial fiber described in an embodiment of the present invention. DETAILED DESCRIPTION

[0018] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art to which this invention belongs. The experimental reagents used in the following examples, unless otherwise specified, are conventional biochemical reagents; the experimental methods described, unless otherwise specified, are conventional methods.

[0019] Tetraethyl orthosilicate, hereinafter referred to as TEOS; tetramethyl orthosilicate, hereinafter referred to as TMOS; tetrabutyl orthosilicate, hereinafter referred to as TPOS.

[0020] TMOS, TEOS, TPOS, sodium dodecylbenzenesulfonate and 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 Reagent Co., Ltd. All chemicals were used without further treatment. Distilled water (ρ = 18.2 MΩ•cm, 25°C) was from a Millipore milli-Q water purification system.

[0021] The present invention will be described in detail below with reference to the embodiments.

[0022] Example 1 A method for preparing a multifunctional rare earth composite antibacterial fiber comprises the following steps: Step 1 is to mix 10g of Ce(NO3)3•6H2O and 12g of tetraethyl orthosilicate evenly, add 180mL of ethanol thereto, transfer the mixture into an ultrasonic microwave reactor, adjust the ultrasonic power to 400W, set the temperature to 60°C, perform ultrasonic-microwave treatment, then add 10g of urea thereto, adjust the pH value of the solution to 9, and introduce N2 protection, add 5mL of polyethylene glycol thereto, and obtain a sol after reaction; Step 2 is to quench the sol with liquid nitrogen, freeze-dry (-50°C, 12h), and dry at 25°C to obtain a gel; Step 3 is to calcine the gel under an inert atmosphere at 300°C for 1.5 hours and then at 600°C for 3 hours at a heating rate of 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration to 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a rare earth composite antibacterial additive; Step 4 is to add 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester particles, mix them evenly, so that the additive is evenly attached to the polyester particles, and then put the mixed polyester particles into an oven, dry them at 80°C, and extrude them at 250°C to obtain rare earth composite antibacterial polyester masterbatch; Step 5 is to mix, melt, and spin (temperature 260° C., rotation speed 2400 rpm) 10 parts of rare earth composite antibacterial polyester masterbatch and 100 parts of polyester chips to obtain the multifunctional rare earth composite antibacterial fiber.

[0023] Comparative Example 1 A method for preparing a multifunctional rare earth composite antibacterial fiber comprises the following steps: Step 1 is to mix 10g of Y(NO3)3•6H2O and 12g of tetraethyl orthosilicate, add 180mL of ethanol thereto, transfer the mixture into an ultrasonic microwave reactor, adjust the ultrasonic power to 400W, set the temperature to 60°C, perform ultrasonic-microwave treatment, then add 10g of urea thereto, adjust the pH value of the solution to 9, and introduce N2 protection, add 5mL of polyethylene glycol thereto, and obtain a sol after reaction; Step 2 is to quench the sol with liquid nitrogen, freeze-dry (-50°C, 12h), and dry at 25°C to obtain a gel; Step 3 is to calcine the gel under an inert atmosphere at 300°C for 1.5 hours and then at 600°C for 3 hours at a heating rate of 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration to 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a rare earth composite antibacterial additive; Step 4 is to add 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester particles, mix them evenly, so that the additive is evenly attached to the polyester particles, and then put the mixed polyester particles into an oven, dry them at 80°C, and extrude them at 250°C to obtain rare earth composite antibacterial polyester masterbatch; Step 5 is to mix, melt, and spin (temperature 260° C., rotation speed 2400 rpm) 10 parts of rare earth composite antibacterial polyester masterbatch and 100 parts of polyester chips to obtain the multifunctional rare earth composite antibacterial fiber.

[0024] Comparative Example 2 A method for preparing a multifunctional rare earth composite antibacterial fiber comprises the following steps: Step 1 is to mix 10g of Ce(NO3)3•6H2O and 12g of tetraethyl orthosilicate evenly, add 180mL of ethanol thereto, transfer the mixed solution into an ultrasonic microwave reactor, adjust the ultrasonic power to 400W, set the temperature to 60°C, perform ultrasonic-microwave treatment, then add 10g of urea thereto, adjust the pH value of the solution to 9, and introduce N2 protection to obtain a sol after the reaction; Step 2 is to quench the sol with liquid nitrogen, freeze-dry (-50°C, 12h), and dry at 25°C to obtain a gel; Step 3 is to calcine the gel under an inert atmosphere at 300°C for 1.5 hours and then at 600°C for 3 hours at a heating rate of 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration to 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a rare earth composite antibacterial additive; Step 4 is to add 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester particles, mix them evenly, so that the additive is evenly attached to the polyester particles, and then put the mixed polyester particles into an oven, dry them at 80°C, and extrude them at 250°C to obtain rare earth composite antibacterial polyester masterbatch; Step 5 is to mix, melt, and spin (temperature 260° C., rotation speed 2400 rpm) 10 parts of rare earth composite antibacterial polyester masterbatch and 100 parts of polyester chips to obtain the multifunctional rare earth composite antibacterial fiber.

[0025] Comparative Example 3 A method for preparing a multifunctional rare earth composite antibacterial fiber comprises the following steps: Step 1 is to mix 10g of Ce(NO3)3•6H2O and 12g of fumed silica uniformly, add 180mL of ethanol thereto, transfer the mixed solution into an ultrasonic microwave reactor, adjust the ultrasonic power to 400W, set the temperature to 60°C, perform ultrasonic-microwave treatment, then add 10g of urea thereto, adjust the pH value of the solution to 9, and introduce N2 protection, add 5mL of polyethylene glycol thereto, and obtain a mixed powder after reaction; Step 2 is to quench the mixed powder with liquid nitrogen, freeze-dry (-50°C, 12h), and dry at 25°C to obtain powder; Step 3 is to calcine the gel under an inert atmosphere at 300°C for 1.5 hours and then at 600°C for 3 hours at a heating rate of 5°C / min. After cooling to room temperature, the calcined powder is added to water to control its concentration to 25%, and added to a sand mill at a sand milling temperature of 25°C, a sand milling speed of 3200 rpm, and a sand milling time of 5 hours to obtain a rare earth composite antibacterial additive; Step 4 is to add 1.5 parts of rare earth composite antibacterial additive to 10 parts of polyester particles, mix them evenly, so that the additive is evenly attached to the polyester particles, and then put the mixed polyester particles into an oven, dry them at 80°C, and extrude them at 250°C to obtain rare earth composite antibacterial polyester masterbatch; Step 5 is to mix, melt, and spin (temperature 260° C., rotation speed 2400 rpm) 10 parts of rare earth composite antibacterial polyester masterbatch and 100 parts of polyester chips to obtain the multifunctional rare earth composite antibacterial fiber.

[0026] like Figure 1 As shown, the SEM image reveals a large number of evenly distributed pores on the material's surface. These pores are formed thanks to the bubble template method, which creates a rich porous structure within and on the material. This porous structure significantly increases the material's specific surface area, providing a larger contact area for the antibacterial reaction, facilitating sufficient contact between rare earth cerium ions and microorganisms, and thus enhancing antibacterial properties. The pore size and distribution are observed to be relatively uniform. This demonstrates that the combined sol-gel and bubble template methods effectively control the reactions and phase separation between the components during the preparation process, allowing for uniform dispersion of the bubble template within the material and avoiding the potential for uneven performance due to localized pore size. Silica serves as the material's matrix, and the image shows that it forms a continuous network structure. This network provides mechanical stability and support for the material, while also providing a foundation for the loading and dispersion of cerium ions. The interaction between the silica network and cerium ions contributes to the material's durable antibacterial properties, as silica protects the cerium ions from the external environment, preventing their rapid loss or inactivation.

[0027] like Figure 2 and Figure 3 As shown in the figure, when it is replaced with yttrium salt, the antibacterial effect is not good. This is because the Ce in cerium nitrate 3+ / Ce 4+Reversible conversion can effectively promote the generation of free radicals and give the material higher reactivity. Other rare earth salts lack this valence change mechanism and find it difficult to maintain the same level of free radical catalytic efficiency. In addition, when the pore-forming agent polyethylene glycol is not added, the system lacks gas as a template, generating a porous structure, reducing the specific surface area, reducing the reaction sites, and subsequently reducing the reactivity. A strategy of controlled hydrolysis of silicate compounds in an alcohol medium is adopted: a sol-gel process is used to achieve uniform assembly of silicon-oxygen bonds in the organic chain, and nano-scale silica particles are formed after high-temperature calcination. These particles not only act as nucleation sites to promote micropore formation, but also construct a multi-level pore structure that is interconnected through spatial cross-linking, significantly improving the specific surface area and surface reactivity of the material, and ultimately achieving a synergistic enhancement of antibacterial properties. However, the use of fumed silica cannot achieve the above effects.

[0028] The white filamentous fibers prepared by the present invention (such as Figure 4 Compared with commercially available brass fibers, it has the advantage of more convenient post-dyeing.

[0029] 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 in the scope of protection of the present invention.

Claims

1. A method for preparing a multifunctional rare earth composite antibacterial fiber, characterized by: The steps include: Step 1 is to mix the cerium salt and the silicate compound uniformly, add a solvent thereto, perform ultrasonic-microwave treatment, then add urea thereto, adjust the pH value of the solution to 8-9, introduce N2 protection, add a pore-forming agent thereto, and obtain a sol after reaction; Step 2 is to quench the sol with liquid nitrogen, freeze-dry, and dry it to obtain a gel; Step 3 is to calcine and sand-mill the gel under an inert atmosphere to obtain a rare earth composite antibacterial additive; Step 4 is adding the rare earth composite antibacterial additive to the polyester particles, mixing them evenly, and extruding to obtain a rare earth composite antibacterial polyester masterbatch; Step 5 is to mix, melt and spin the rare earth composite antibacterial polyester masterbatch with polyester chips to obtain the multifunctional rare earth composite antibacterial fiber.

2. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: The solid-liquid ratio of the cerium salt, silicate compound, solvent, urea and pore-forming agent in step 1 is 6-15g:10-15g:150-200mL:5-12g:1-5mL.

3. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 2, characterized in that: 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 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; the solvent in step 1 is methanol or ethanol.

4. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: The ultrasonic power of the ultrasonic-microwave step in step 1 is 300-450W, and the microwave temperature is 50-70°C.

5. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: 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.

6. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: The calcination step in step 3 is specifically as follows: the temperature of the first section is 200-350°C, the time is 1-2 hours, the temperature of the second section is 500-700°C, the time is 2-4 hours, and the heating rate is 5-10°C / min; the inert atmosphere in step 3 is argon; the temperature of the sand grinding step in step 3 is 20-30°C, the time is 4-6 hours, and the speed is 2600-3800 rpm.

7. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: 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°C.

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

10.

9. The method for preparing the multifunctional rare earth composite antibacterial fiber according to claim 1, characterized in that: The cavity temperature of the spinning step in step 5 is 220-270° C., and the rotation speed is 2300-2500 rpm.

10. A multifunctional rare earth composite antibacterial fiber prepared by the preparation method according to any one of claims 1 to 9.

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