Preparation method and application of inorganic composite powder and reversible thermochromic antibacterial silicone fiber

Abstract

This invention discloses an inorganic composite powder and a method for preparing and applying reversible thermochromic antibacterial organosilicon fibers. The inorganic composite powder is TiO2@AgI, wherein AgI is dispersed and loaded in nanoscale form on a TiO2 substrate, the mass ratio of AgI to TiO2 is 1:(1~50), and the particle size is 100nm~5μm. By dispersing AgI in nanoscale form on a TiO2 substrate to obtain a heterojunction, it possesses both reversible thermochromic properties and antibacterial properties. When added to and spun into organosilicon fibers, reversible thermochromic properties with cyclic color change at medium to high temperatures are achieved, which are antibacterial, non-toxic, and have high strength. This invention overcomes the technical bottlenecks of poor thermal stability, low color change threshold temperature, and low response sensitivity of existing RTFs, improves the low air permeability of existing organosilicon antibacterial dressings, and compensates for their limited applicability. It has important practical significance and application value for expanding the application fields of organosilicon materials.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon fiber technology, and more specifically, relates to a method for preparing and applying an inorganic composite powder and a reversible thermochromic antibacterial organosilicon fiber. Background Technology

[0002] In recent years, reversible thermochromic fibers (RTFs) have shown great promise in areas such as human health monitoring, thermal management, intelligent anti-counterfeiting, temperature visualization, and warnings due to their intelligent external response color-changing function. RTFs are intelligent flexible materials that can display different colors in response to changes in ambient temperature. They combine the flexibility and ease of processing of fibers with intelligent color-changing in response to external stimuli, and can also be recycled multiple times. Compared with traditional contact temperature measurement, RTFs have the advantage of quickly determining the temperature range through the color change of the fiber itself, thus attracting great attention from researchers. However, most fiber substrates suffer from poor thermal stability and low color-changing threshold temperatures, meaning that current RTFs are only suitable for low-temperature environments. This greatly limits the application of RTFs, and some materials may even be toxic to organisms.

[0003] Few RTFs (Regenerative Thermal Fibers) can achieve color-changing properties at high temperatures, mainly due to the poor heat resistance and thermal stability of common fiber materials. Currently, commercially available color-changing fibers are primarily polyester fibers, and the color-changing materials used are mainly organic. Therefore, the color-changing fibers produced and sold are only suitable for low-temperature color-changing applications, such as human thermal management and medical fields. Research and development, and the market for medium- and high-temperature, especially high-temperature, color-changing fibers are lacking.

[0004] Organosilicon materials have become the preferred material in many emerging technology fields due to their excellent high-temperature resistance. Developing organosilicon materials into flexible, processable, and reversible thermochromic fibers holds promise for further expanding their applications in high-temperature environments.

[0005] Meanwhile, as a common high-performance material, organosilicon materials have advantages such as high tensile strength, good flexibility, corrosion resistance, and good biocompatibility, and are therefore widely used in the fields of biomedical materials. However, the following problems still exist in the process of use: (1) Although a considerable number of reports have confirmed that organosilicon polymers have excellent biocompatibility, biomedical organosilicon materials are usually in direct contact with human tissues during use, which can easily cause bacterial adhesion and exist in the form of biofilm, thereby protecting the internally embedded bacteria from antibacterial treatment and host immune defense, which seriously limits their clinical application; (2) In recent years, most of the antibacterial organosilicon materials reported are in the form of gels and films. Although this has solved the shortcomings of organosilicon materials in terms of lack of antibacterial ability to a certain extent, the air permeability of such materials usually depends on the formulation and structural design. Materials with poor air permeability may increase the risk of secondary tissue infection.

[0006] In contrast, fabricating antibacterial silicone materials into fiber form can endow silicone antibacterial materials with excellent tensile strength and resilience. Furthermore, due to their unique flexibility, processability, and structural designability, fiber materials can be combined with various functional materials to prepare advanced composite materials with tunable properties. This composite strategy not only retains the mechanical advantages and flexibility of the fibers themselves but also endows the materials with new functions through component synergistic effects, thereby meeting diverse application needs and making them more suitable for scenarios involving repeated deformation, such as antibacterial bandages and antibacterial protective gear. If silicone antibacterial fibers are further constructed into fabrics through weaving processes, a perfect balance between multi-scale breathable structure and highly efficient antibacterial performance can be achieved, thus meeting the stringent requirements of high-end applications such as medical protection and smart wearables. However, because silicone fibers are cross-linked polymers, their production and processing are relatively difficult. Currently, there are few reports on the fiberization of silicone materials, and research reports on silicone antibacterial fibers are even rarer. Summary of the Invention

[0007] The purpose of this invention is to address the above-mentioned shortcomings by providing a method for preparing and applying an inorganic composite powder and reversible thermochromic antibacterial organosilicon fibers. This inorganic composite powder is prepared by dispersing AgI in nano-form on a TiO2 substrate to obtain a heterojunction, thus possessing both reversible thermochromic properties and antibacterial properties. When added to and spun into organosilicon fibers, it achieves reversible thermochromic properties with cyclic color change at medium to high temperatures, exhibiting antibacterial and non-toxic characteristics as well as high strength. This overcomes the technical bottlenecks of existing RTFs, such as poor thermal stability, low color change threshold temperature, and low response sensitivity. It also improves the low air permeability and limited applicability of existing organosilicon antibacterial dressings, and has significant practical significance and application value for expanding the application fields of organosilicon materials.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution: In a first aspect, the present invention provides an inorganic composite powder, wherein the inorganic composite powder is TiO2@AgI, wherein AgI is dispersed and loaded in nano-form on a TiO2 substrate, and the mass ratio of AgI to TiO2 is 1:(1~50); the particle size of TiO2@AgI is 100nm~5μm.

[0009] Preferably, the mass ratio of AgI to TiO2 in TiO2@AgI is 1:(5~20), more preferably 1:(10~11; the particle size of TiO2@AgI is 100 nm~500 nm.

[0010] Preferably, the TiO2 is a rutile phase, anatase phase, or a mixture of both phases. More preferably, the TiO2 is a rutile phase.

[0011] In a second aspect, the present invention also provides a method for preparing the inorganic composite powder material described in the first aspect, comprising: TiO2@AgI powder was prepared by mixing TiO2, KI and AgNO3 in deionized water and using a dissolution-precipitation method. The mass ratio of TiO2, KI and AgNO3 is 1: (0.95~1.05): (5~50), and the reaction time of the dissolution-precipitation method is 5 min~120 min.

[0012] Preferably, the mass ratio of TiO2, KI and AgNO3 is 1: (0.98~1.02): (10~15), and the reaction time is 5 min~60 min; more preferably, the reaction time is 5 min~30 min.

[0013] Preferably, after the dissolution-precipitation reaction is completed, the obtained product is ball-milled using a ball mill.

[0014] Preferably, the ball milling parameters include: a ball milling time of 20 min to 60 min, a rotation speed of 200 rpm to 600 rpm, and a ball-to-material ratio of (1.4 to 4.1):1.

[0015] Thirdly, the present invention also provides a reversible thermochromic antibacterial silicone fiber, wherein the raw materials of the silicone fiber include a silicone oil spinning solution, the TiO2@AgI powder material described in the first aspect, a catalyst, an inhibitor, and a curing accelerator; the silicone oil spinning solution includes vinyl silicone oil and hydrogen-based silicone oil in a mass ratio of 1:(0.8~1.4), the vinyl silicone oil includes terminal vinyl silicone oil and side vinyl silicone oil, and the amount of side vinyl silicone oil added is 0~20 wt%; the amount of TiO2@AgI powder material added is 0.5 wt%~4.5 wt% of the total amount of silicone oil spinning solution; the amount of catalyst, inhibitor, and curing accelerator added is 0.1 wt%~1 wt% of the total amount of silicone oil spinning solution.

[0016] Preferably, the mass ratio of the vinyl silicone oil to the hydrogen-based silicone oil is 1:(1.1~1.2), the amount of vinyl silicone oil added in the vinyl silicone oil is 14 wt%~16 wt%, and the amount of TiO2@AgI powder material added is 1 wt%~5 wt% of the total amount of silicone oil.

[0017] Preferably, the vinyl-terminated silicone oil is a divinyl-terminated phenyl silicone oil with a viscosity of 500 cp to 3000 cp and a vinyl content of 0.8% to 1.2%; it includes any mixture of one or more of α,ω-vinyl polymethylphenylsiloxane, or α,ω-vinyl poly(methylphenylsiloxane-dimethylsiloxane) or α,ω-vinyl poly(dimethylsiloxane-diphenylsiloxane); more preferably, it is α,ω-vinyl polymethylphenylsiloxane with a viscosity of 950 to 1050 cp and a vinyl content of 0.8% to 1.2%.

[0018] Preferably, the side-vinyl silicone oil is an end-side polyvinylphenyl silicone oil with a viscosity of 500 cp to 10000 cp and a vinyl content of 2.3% to 2.7%; it includes one or any mixture of two of α,ω-vinyl poly(methylphenylsiloxane-methylvinylsiloxane) or α,ω-vinyl poly(phenylvinylsiloxane-methylphenylsiloxane); preferably, it is α,ω-vinyl poly(methylphenylsiloxane-methylvinylsiloxane) with a viscosity of 5000 cp and a vinyl content of 2.3% to 2.7%.

[0019] Preferably, the hydrogen-based silicone oil is a side-containing hydrogen silicone oil, comprising α,ω-dimethyl polymethylhydrosiloxane, with a viscosity of 80 cp to 100 cp, and the hydrogen content in the hydrogen-based silicone oil is 0.36% to 1.6%; more preferably, the hydrogen content is 0.75%.

[0020] Preferably, the catalyst is a platinum catalyst, including any one of Speier catalyst and Karstedt catalyst, with a platinum concentration of 1000 ppm to 10000 ppm; more preferably, a Karstedt catalyst is used, with a platinum concentration of 3000 ppm; the inhibitor can be acetylenol, 2-methyl-3-butanol-2-ol or butynediol, preferably acetylenol, and its solvent can be ethanol or isopropanol, preferably isopropanol, with an inhibitor concentration of 1000 ppm to 10000 ppm, more preferably 4500 ppm to 5500 ppm; the curing accelerator is a borate ester, including trimethyl borate, triethyl borate, tributyl borate or pinacol diborate, with a curing accelerator concentration of 1000 ppm to 10000 ppm.

[0021] Fourthly, the present invention also provides a method for preparing the reversible thermochromic antibacterial organosilicon fiber described in the third aspect, comprising: TiO2@AgI powder material was prepared by mixing TiO2, KI and AgNO3 in deionized water and using a dissolution-precipitation method. Vinyl silicone oil and hydrogen-based silicone oil are mixed evenly in a certain proportion to prepare a silicone oil spinning solution; The TiO2@AgI powder material was added to the silicone oil spinning solution and dispersed evenly. A catalyst, an inhibitor, and a curing accelerator were added to a silicone oil spinning solution containing TiO2@AgI powder, and the mixture was stirred to obtain a spinning solution prepolymer. The above-mentioned spinning solution prepolymer is added to the spinning equipment, and cross-linking and curing are induced by air heating, and then spun into fibers.

[0022] Preferably, after the dissolution-precipitation reaction is completed, the obtained product is ball-milled using a ball mill.

[0023] Preferably, the ball milling parameters include: a ball milling time of 20 min to 60 min, a rotation speed of 200 rpm to 600 rpm, and a ball-to-material ratio of (1.4 to 4.1):1.

[0024] Preferably, the silicone oil spinning solution is prepared at a temperature of 20°C to 50°C and a stirring rate of 100 rpm to 1000 rpm; the temperature for heat-induced crosslinking and curing is 150°C to 250°C; more preferably, the silicone oil spinning solution is prepared at a temperature of 25°C and a stirring rate of 140 rpm to 160 rpm; the temperature for heat-induced crosslinking and curing is 200°C to 220°C.

[0025] Preferably, the spinning equipment includes a constant pressure injection pump, a spinning head and a heat insulation support, a heating sleeve, a temperature control device, and a collection device. The spinning solution prepolymer is propelled into the spinning head by the constant pressure injection pump and output to the collection device through the spinning head to solidify. The heating sleeve is fitted over the spinning head. The temperature control device is used to adjust the temperature of the heating sleeve so that the spinning solution is stretched and pulled while being induced to crosslink and solidify in situ by air heating when passing through the spinning head.

[0026] Fifthly, the present invention also provides the application of the reversible thermochromic antibacterial silicone fiber described in the first aspect in the preparation of reversible thermochromic materials. Specifically, the prepared reversible thermochromic material can be used for thermal management, intelligent anti-counterfeiting, high-temperature scene warnings, and color visualization, etc.

[0027] Sixthly, the present invention also provides the application of the reversible thermochromic antibacterial silicone fiber described in the first aspect in the preparation of antibacterial materials. Specifically, the prepared antibacterial materials can be used in antibacterial dressings, antibacterial bandages, antibacterial protective gear, smart wearables, etc.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows: The inorganic composite powder provided by this invention possesses both reversible thermochromic properties and antibacterial properties. On the one hand, by using AgI as a thermochromic material and TiO2 as a white background, the composite powder material exhibits distinct thermochromic properties. Simultaneously, the silver salt disperses the nanomaterials, providing excellent rapid thermochromic response and achieving very high temperature response sensitivity. On the other hand, the composite powder can effectively suppress the recombination of photogenerated carriers, overcoming the shortcomings of AgI's poor photostability and easy decomposition while improving the visible light photocatalytic utilization rate of TiO2. The coexistence of AgI / TiO2 heterojunction photocatalysis and AgI metal ion release mechanisms achieves a synergistic antibacterial effect through a dual-mode approach of photocatalytic sterilization and metal ion release antibacterial action.

[0029] This invention adds the inorganic composite powder and spins it to obtain organosilicon fibers, enabling them to achieve reversible thermochromic changes at medium to high temperatures. These fibers are antibacterial, non-toxic, and have high strength. This invention overcomes the technical bottlenecks of existing RTFs, such as poor thermal stability, low color change threshold temperature, and low response sensitivity. It also improves the low air permeability and limited applicability of existing organosilicon antibacterial dressings, and has significant practical significance and application value for expanding the application fields of organosilicon materials.

[0030] The present invention uses a hydrosilylation reaction and air heating to induce in-situ curing of the spinning solution into fibers to obtain reversible thermochromic antibacterial silicone fibers with high strength. The preparation process is more non-toxic and environmentally friendly, simple, short cycle, and can be continuously produced. Attached Figure Description

[0031] Figure 1 Microstructure characterization of TiO2@AgI powder prepared in Example 1; wherein, (a1)~(a3) are TiO2@AgI (11:1) SEM images and particle size distribution calculations; (b1)~(b3) are TiO2@AgI (11:1) TEM image; (c) is TiO2@AgI (11:1) The distribution of elements; Figure 2 Microstructure characterization of the reversible thermochromic antibacterial silicone fiber prepared in Example 1; wherein, (c1) is TiO2@AgI under ultra-depth-of-field three-dimensional microscopy and SEM. (11:1) The longitudinal morphology of @SiF-2; (c2) is TiO2@AgI (11:1) White light image of @SiF-2; (c3) TiO2@AgI under ultra-depth-of-field 3D microscope and SEM. (11:1) Cross-sectional morphology of @SiF-2; Figure 3The image shows the surface elemental distribution of the reversible thermochromic antibacterial silicone fiber prepared in Example 1; where (a) is the elemental distribution of the fiber cross section; and (b) is the elemental distribution of the fiber longitudinal direction. Figure 4 Comparison of antibacterial properties between raw cotton and the reversible thermochromic antibacterial silicone fiber prepared in Example 1; Figure 5 Comparison of antibacterial rate test results between raw cotton and the reversible thermochromic antibacterial silicone fiber prepared in Example 1; Figure 6 The results of in vitro cytotoxicity tests on the reversible thermochromic antibacterial silicone fiber prepared in Example 1 are shown. Among them, (a) shows the cell survival status of L929 cells after culturing different concentrations of extracts of antibacterial powder prepared in Example 1 with the control group and the cell viability after 12 h. Figure 7 The photoelectric properties of TiO2@AgI powder and reversible thermochromic antibacterial silicone fiber prepared in Example 1 are characterized; wherein, (a) is the semiconductor energy band gap (Tauc) diagram of AgI, TiO2 and TiO2@AgI powder; (b) is the ultraviolet-visible light reflectance spectrum of AgI, TiO2 and TiO2@AgI powder; (c) is the ultraviolet-visible light reflectance spectrum of TiO2@AgI powder and reversible thermochromic antibacterial silicone fiber; Figure 8 This is a diagram illustrating the antibacterial mechanism of the reversible thermochromic antibacterial silicone fiber described in this invention. Figure 9 The photostability of the products obtained in Example 1 and Comparative Example 1 is compared. Among them, (a) is a comparison of the pure AgI spinning solution prepared in Comparative Example 1 and the composite spinning solution prepared in Example 1 after being placed under light for 15 min; (b) is a photo of the organosilicon fiber prepared in Comparative Example 1 turning black after being placed for 24 h. Figure 10 The images show the color-changing optical photographs of the organosilicon fibers prepared in Comparative Example 1; where (a) is before low-temperature color change, (b) is after high-temperature color change, and (c) is a comparison image before and after being placed at room temperature for 24 hours. Figure 11 The effect of different TiO2 addition amounts on the color-changing properties of TiO2@AgI powder is shown; the left side is the color patch diagram of TiO2@AgI under different TiO2 addition amounts, and the right side is the color parameter diagram of TiO2@AgI under different TiO2 addition amounts. Figure 12 The effect of TiO2@AgI powder particle size distribution on the mechanical properties of reversible thermochromic antibacterial silicone fiber is shown; (a) is a comparison of tensile strength of different embodiments; (b) is the particle size distribution of Example 9; (c) is the particle size distribution of Examples 10-17. Figure 13 This is a verification diagram of the rapid color-changing characteristics of the reversible thermochromic antibacterial silicone fiber prepared in Example 18. Figure 14 This is a diagram illustrating the color change sensitivity of the reversible thermochromic antibacterial silicone fiber prepared in Example 18. Figure 15 For different TiO2@AgI (11:1) The effect of addition amount on the tensile properties of reversible thermochromic antibacterial silicone fiber; wherein, (a) is the effect curve of different addition amounts on the tensile strength of fiber; (b) is the stress-strain curve of fiber obtained in Example 18; (c) is the performance graph of fiber obtained in Example 18 after 150 cycles at 100% elongation. Figure 16 For different TiO2@AgI (11:1) The effect of addition amount on the color-changing properties of reversible thermochromic antibacterial silicone fiber; where (a) represents different amounts of TiO2@AgI (11:1) (a) Effect of addition amount on fiber color difference value; (b) Color difference comparison of fiber obtained in Example 18 at 20 °C and 150 °C. Detailed Implementation

[0032] In the preparation of reversible thermochromic antibacterial organosilicon fibers, this invention uses TiO2@AgI as a functional material. The doping amount of TiO2@AgI not only affects the color-changing and antibacterial properties, but also the mechanical properties of the fiber. Therefore, under the premise of ensuring that the spinning solution is completely cured under high temperature conditions, the mass ratio of TiO2 and AgI and the doping amount of TiO2@AgI are adjusted to obtain organosilicon fibers with high strength, excellent color-changing and antibacterial properties, thereby broadening the application of organosilicon materials in high-temperature scene detection and temperature visualization, as well as biomedical materials.

[0033] Preferred embodiments of the present invention will now be described in more detail with reference to the accompanying drawings and specific examples.

[0034] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used are commercially available.

[0035] The raw materials used in the specific embodiments are as follows: Vinyl-terminated silicone oil: α,ω-vinyl polymethylphenylsiloxane, 1000cp, Guoyan Chemical New Materials Co., Ltd.; Side-bound vinyl silicone oil: α,ω-vinyl poly(methylphenylsiloxane-methylvinylsiloxane), 5000 cp, Guoyan Chemical New Materials Co., Ltd.; Hydrogen-based silicone oil: α,ω-dimethyl polymethylhydrosiloxane, hydrogen content 0.75%, Shenzhen Jipeng Silicon Fluorine Materials Co., Ltd.; Inhibitor: Weigh 0.05 g of acetylenol (Shanghai Aladdin Biochemical Technology Co., Ltd.) and add it to isopropanol. Dilute to 10 mL with a volumetric flask to prepare a solution with a concentration of 5000 ppm. Curing accelerator: Weigh 0.05 g of dipinacol diboronate (Shanghai Aladdin Biochemical Technology Co., Ltd.), add isopropanol, and dilute to 10 mL with a volumetric flask to prepare a solution with a concentration of 5000 ppm; Catalyst: Karstedt catalyst, platinum content 3000 ppm, Shenzhen Kejunchi Industrial Co., Ltd.

[0036] The measurement methods in the following embodiments include: (1) The mechanical properties of the prepared silicone fibers were tested using an INSTRON-3365 dual-arm material testing machine. According to the national standard GB / T 14337-2022 for testing the tensile properties of short chemical fibers, the fibers were cut to a length of 4 cm and both ends were wrapped with labels. The sensor used in the test had a range of 0~8 N, and the tensile speed was 4 cm·min. -1 The spacing was 2 cm. To ensure more accurate measurements, each fiber sample was tested an average of 20 times to obtain the average tensile strength and elongation at break. Furthermore, keeping the fiber stretching rate constant, the fibers were subjected to 150 cycles of stretching at 100% elongation to study the fatigue resistance of the silicone fibers.

[0037] (2) Linear density is one of the most important indicators used to characterize the thickness of fibers. The commonly used unit is tex (N). t (tex), tex N dt (dtex) and denier ND. Measure and cut a length of silicon fiber, accurately weigh the fiber on an electronic balance, and then calculate the linear density of the silicone fiber using the following formula: ; Where: L is the length of the fiber (m), and m is the mass of the fiber (g).

[0038] (3) The colors of inorganic composite powder and organosilicon fiber at different temperatures were captured under the D65 standard illuminator specified by the International Commission on Illumination. The captured photos were imported into Adobe Photoshop 2023 software for color parameter analysis. The color change sensitivity and rapid color change characteristics were analyzed together with infrared thermograms.

[0039] (4) The antibacterial performance test was conducted according to the national standard GB / T 20944.3-2008, Part III, the shaking method. Using pure cotton fabric (CF) as a control, silicone fibers and CF were washed according to standard and cut into 5 mm short fibers and 5 mm × 5 mm fragments, respectively, and placed in an autoclave for 15 min. Subsequently, the antibacterial fibers and CF were placed in Erlenmeyer flasks, and a certain amount of PBS buffer and inoculated bacterial solution were added. The bacterial strains were Staphylococcus aureus and Escherichia coli. The mixture was sterilized at 24 °C ± 1 °C at 150 r·min. -1 Shake for 18 h. Take 1 mL of solution from each flask, dilute it, and spread it evenly in a petri dish for incubation. Finally, count and photograph the colonies of both bacterial strains. The viable cell concentration K and inhibition rate Y are calculated using the following formulas: ; ; in, K viable bacterial concentration (CFU·mL) -1 ), Z This is the average colony count of the two plates. R This is the dilution factor. Y The antibacterial rate of the sample is %. W t The average concentration of viable bacteria (CFU·mL) in the flask after 18 h of shaking contact with the control sample CF is shown. -1 ), Q t The average concentration of viable bacteria in the flask after 18 h of shaking contact with the fiber (CFU·mL) -1 ).

[0040] (5) Mouse fibroblasts (L929) were used to evaluate the cytotoxicity of organosilicon fibers. L929 cells were cultured in a medium containing 10% fetal bovine serum, 1% P / S penicillin-streptomycin, and 89% MEM at 37 °C and 5% CO2. Organosilicon fibers were cut into certain pieces (10 mg, 20 mg, 40 mg, and 100 mg), autoclaved, and then added to 10 mL of medium and soaked at 37 °C for 24 h. L929 cells in the logarithmic growth phase were treated according to the above grouping and cultured in a 5% CO2, 37 °C incubator for 12 h, and photographed under a 100x white light microscope. The medium was removed, the wells were washed three times with PBS, and 10% CCK8 medium was added at 100 μL / well. The cells were then cultured in a 5% CO2, 37 °C incubator for 2 h, and the optical density (OD) at 450 nm was detected using a microplate reader. L929 cell relative viability ( R Calculate according to the following formula: ; in, R It is relative cell viability (%). OD sample It is the OD value of the experimental sample. OD background It is the background OD value. OD 0 This is the mean OD value of the control group.

[0041] Example 1: This embodiment provides a reversible thermochromic antibacterial silicone fiber, the preparation method of which includes the following steps: S1: Synthesis of TiO2@AgI powder Weigh 11 g of TiO2 into a clean container, then add 500 mL of deionized water and stir at 1000 rpm for 10 min to fully disperse the TiO2. Weigh 0.80 g of AgNO3 and pour it into the deionized water, stirring at 1000 rpm for 10 min to fully dissolve it. Then, weigh 0.78 g of KI into a clean container, add 10 mL of deionized water, sonicate to dissolve, and pour the solution into the AgNO3 solution. React in the dark for 30 min. Filter and dry the resulting TiO2@AgI dispersion for later use. This product is denoted as TiO2@AgI. (11:1) .

[0042] S2: Preparation of silicone oil spinning solution Take a clean container and add 32.5 g of α,ω-vinyl polymethylphenylsiloxane (1000 cp), 4.8 g of α,ω-vinyl poly(methylphenylsiloxane-methylvinylsiloxane) (5000 cp) and 2.7 g of α,ω-dimethyl polymethylhydrosiloxane (0.75% hydrogen content) in sequence. Mix the silicone oil evenly at a stirring speed of 150 rpm to obtain the silicone oil spinning solution.

[0043] S3: Add TiO2@AgI to the silicone oil spinning solution 0.8 g (2% of the mass of the silicone oil spinning solution) of TiO2@AgI prepared in S1 was added to the silicone oil spinning solution prepared in S2, and the mixture was stirred at a stirring rate of 2000 rpm for 6 h to fully disperse TiO2@AgI in the silicone oil spinning solution.

[0044] S4: Prepolymer Add 0.1% (5000 ppm) of the inhibitor ethynylcyclohexanol (equivalent to 0.1% of the total mass of silicone oil) to the silicone oil spinning solution obtained in S3, and stir for 5 min to ensure that the inhibitor is evenly distributed in the spinning solution; then add 3000 ppm of platinum catalyst Karstedt and 0.1% (equivalent to 0.1% of the total mass of silicone oil) of dipinacol diboronate, control the system temperature at 25℃, and stir at 150 rpm for about 15 min to prepolymerize the spinning solution to a spinnable state, thus obtaining the spinning solution prepolymer.

[0045] S5: High-temperature air-induced cross-linking and curing into filaments After fully degassing the spinning solution prepolymer prepared by S4, it was added to the spinning equipment and injected into a 50 mL syringe, which was then clamped onto a constant pressure injection pump. The injection speed of the constant pressure injection pump was set to 0.65 mL / min. -1 The actual heating temperature at the center of the heating sleeve was measured to be approximately 200℃~220℃. When the spinning solution prepolymer passes through the heating sleeve at a uniform speed, it undergoes stretching and in-situ cross-linking and curing, and is fully cured upon entering the rotating collection cage, resulting in a reversible thermochromic antibacterial silicone fiber product, codenamed TiO2@AgI. (11:1) @SiF-2.

[0046] The inorganic composite powder TiO2@AgI prepared in this embodiment is... (11:1) For its morphology and structure, see Figure 1 As can be seen from the figure, under the SEM image, TiO2@AgI (11:1) At the nanoscale, exhibiting a random state, the scattered black particles in the TEM image are AgI, and the surface elemental distribution shows TiO2@AgI. (11:1) It is composed of four elements: Ti, O, Ag, and I.

[0047] The reversible thermochromic antibacterial organosilicon fiber TiO2@AgI prepared in this embodiment is shown in the figure. (11:1) For the microstructure of @SiF-2, please refer to... Figure 2 It can be seen that the fiber cross-section is a regular circle, and the longitudinal direction is smooth without wrinkles. The diameter of the fiber was measured at 10 different points on the same fiber, and the average diameter of the fiber was calculated to be 300±14 μm. Figure 3 The surface element distribution shown indicates that in addition to Ti, O, Ag and I elements, it also contains Si and C elements; the color difference before and after the thermal color change of the fiber is calculated to be 25.72.

[0048] The reversible thermochromic antibacterial organosilicon fiber TiO2@AgI prepared in this embodiment was evaluated using Escherichia coli and Staphylococcus aureus. (11:1) For the antibacterial properties of @SiF-2, see [link to documentation]. Figure 4 and Figure 5 It can be seen that TiO2@AgI (11:1) @SiF-2 showed no visible colonies in its culture medium at different dilutions, demonstrating excellent antibacterial properties with an inhibition rate of 99.99%. Furthermore, as... Figure 6 As shown, TiO2@AgI was also observed in in vitro cytotoxicity tests. (11:1) After co-culturing L929 cells with different concentrations of @SiF-2 extract for 12 h, the cells all showed high activity, with cell viability reaching over 98%, demonstrating its excellent biocompatibility.

[0049] The antibacterial mechanism of the reversible thermochromic antibacterial organosilicon fiber described in this invention is as follows: Figure 7 As shown: After AgI and TiO2 form a heterojunction, the CB of TiO2 is located between the VB and CB of AgI; when irradiated by light with an energy higher than its own Eg, electrons on the VB of AgI are excited and jump to the CB to generate electrons. cb - And leave h on the price band vb + This refers to photogenerated carriers; subsequently, electrons located on the CB of AgI migrate to the CB of TiO2, while h vb + The O2 then remains on the VB of AgI. Since TiO2@AgI is uniformly dispersed within the fiber, according to thermodynamic principles, the O2 adsorbed on the fiber surface will capture e-. - Formation of superoxide radical anions (·O2) - ), and h + This will cause H2O or OH to be released. - The two free radicals generated after conversion to ·OH are highly reactive and undergo redox reactions upon contact with *Escherichia coli* and *Staphylococcus aureus*. The reactive oxygen species (ROS) can penetrate the bacterial cell wall, interfering with bacterial respiration and electron transport systems, thus rapidly killing the bacteria. AgI can also assist in antibacterial activity in dark environments. The solubility product constant of AgI is Ksp = 8.3 × 10⁻¹ 7 It can slowly release Ag + A small amount of Ag exists + When it comes into contact with microorganisms, it can penetrate into the cell membrane of the microorganisms under the microdynamic effect and react with the -SH on the proteins in the microorganisms, causing the microorganisms to synthesize DNA and eventually kill them.

[0050] from Figure 7 As can be seen from the Tauc plot in (a), AgI, TiO2, and TiO2@AgI (11:1)The band gap values ​​of the three materials were 2.73 eV, 2.97 eV, and 2.85 eV, respectively, which are close to the theoretical values. Secondly, a lower band gap (Eg) indicates a smaller energy difference between the valence band (VB) and conduction band (CB), making it easier for photogenerated carriers to recombine under illumination. It was observed that the band gap of pure AgI was only 2.73 eV, making it highly susceptible to Ag particle formation due to electron-hole pair recombination, leading to material darkening and decreased gloss. In contrast, the composite TiO2@AgI... (11:1) The band gap width has been increased; from Figure 7 (b) The UV-Vis diffuse reflectance spectrum shows that pure AgI absorbs light in the visible range, indicating that it is prone to decomposition under normal conditions; from Figure 7 As can be seen in (c), TiO2@AgI powder and TiO2@AgI (11:1) The absorption spectra of @SiF-2 are basically the same, indicating that the structure of the organosilicon fiber sample after incorporating TiO2@AgI powder has not changed. Since both TiO2@AgI powder and organosilicon fiber materials have good biocompatibility, TiO2@AgI... (11:1) @SiF-2 is also non-toxic to biological cells and can be used safely.

[0051] The present invention verifies the effect of TiO2 addition amount on the properties of reversible thermochromic antibacterial organosilicon fiber through the following examples and comparative examples.

[0052] Comparative Example 1: This comparative example provides an organosilicon fiber whose preparation method does not include the synthesis of TiO2@AgI powder. Except for replacing TiO2@AgI powder with AgI powder in the addition of silicone oil spinning solution, the remaining steps are all the same as in Example 1. The resulting organosilicon fiber product is designated as AgI@SiF.

[0053] The tensile strength of the silicone antibacterial fiber produced under this process was measured to be 0.81 cN·tex using a dual-arm material testing machine. -1 The antibacterial rate of the fiber was 81.12%, and the color difference before and after thermochromic change was 2.06. Since the organosilicon fiber prepared in this comparative example only has one antibacterial mechanism of anion precipitation, its antibacterial effect is far inferior to that of the reversible thermochromic antibacterial organosilicon fiber with added TiO2@AgI composite powder.

[0054] from Figure 9 As can be seen in (a), the spinning solution containing pure AgI turns black after 15 minutes under indoor light, while the solution containing TiO2@AgI turns black. (11:1)The spinning solution remained almost unchanged, exhibiting excellent photostability. In contrast, TiO2's absorption spectrum is mainly in the ultraviolet region, with a visible light utilization rate of less than 4%. This typically requires ultraviolet excitation to generate electron-hole pairs to produce antibacterial function, which is a demanding condition. The composite TiO2@AgI... (11:1) The absorption spectrum of the composite material shows a red shift compared to pure AgI, indicating that the utilization rate of visible light is improved, and it exhibits antibacterial function under visible light irradiation; from Figure 9 As can be seen in (b), the fiber prepared by directly adding AgI to the spinning solution gradually turns black after being left for 24 hours.

[0055] from Figure 10 (a) Before low-temperature color change and (b) After high-temperature color change, it can be seen that compared with AgI loaded on the TiO2 surface and dispersed as nanoparticles, due to the lack of a white TiO2 background, the color difference caused by directly adding AgI under the same dosage is much smaller than that caused by loading TiO2. Without a titanium dioxide background, the color at high temperature is not bright; while from... Figure 10 As can be seen in (c), the organosilicon fibers spun by directly adding AgI powder turn black after being placed at room temperature for 24 hours, indicating that their storage stability is poor.

[0056] Example 2: Referring to Example 1, the 11 g TiO2 in S1 was replaced with 10 g TiO2, and other conditions and operating steps were the same. The prepared sample was designated as TiO2@AgI. (10:1) @SiF-2.

[0057] Example 3: Referring to Example 1, the 11 g TiO2 in S1 was replaced with 9 g TiO2, and other conditions and operating steps were the same. The prepared sample was designated as TiO2@AgI. (9:1) @SiF-2.

[0058] Example 4: Referring to Example 1, the 11 g TiO2 in S1 was replaced with 7.5 g TiO2, and other conditions and operating steps were the same. The prepared sample was designated as TiO2@AgI. (7.5:1) @SiF-2.

[0059] Example 5: Referring to Example 1, the 11 g TiO2 in S1 was replaced with 5 g TiO2, and other conditions and operating steps were the same. The prepared sample was designated as TiO2@AgI. (5:1) @SiF-2.

[0060] Example 6: Referring to Example 1, the 11 g TiO2 in S1 was replaced with 12.5 g TiO2, and other conditions and operating steps were the same. The prepared sample was designated as TiO2@AgI. (12.5:1) @SiF-2.

[0061] Example 7: Referring to Example 1, 11 g TiO2 in S1 was replaced with 15 g TiO2, while other conditions and operating steps remained the same. The prepared sample was designated TiO2@AgI. (15:1) @SiF-2.

[0062] Example 8: Referring to Example 1, the 11 g TiO2 in S1 was replaced with 20 g TiO2, and other conditions and operating steps were the same. The prepared sample was designated as TiO2@AgI. (20:1) @SiF-2.

[0063] Figure 11 The images show color patches (left) and color parameters (right) of TiO2@AgI powder with different TiO2 addition amounts. When the TiO2 addition amount is 11 g, the overall color difference of the thermochromic powder reaches its maximum value of approximately 35.33. The color difference of the other batches of thermochromic powder is less than 30, and the color difference of the prepared fibers before and after color change is poor. This is sufficient to show that when the TiO2 addition amount is 11 g, TiO2@AgI powder can achieve the best color-changing performance.

[0064] Meanwhile, calculations showed that the reversible thermochromic antibacterial silicone fiber achieved optimal antibacterial performance when the TiO2 addition amount was 11 g; the antibacterial rate of the antibacterial fibers obtained in other batches was all below 99.99%, which is sufficient to demonstrate that TiO2@AgI (11:1) @SiF-2 has the best antibacterial properties.

[0065] This invention analyzes TiO2@AgI through the following embodiments. (11:1) The influence of particle size and distribution on fiber mechanical properties.

[0066] Example 9: This embodiment provides a reversible thermochromic antibacterial silicone fiber, the preparation method of which includes the following steps: S1: Synthesis of TiO2@AgI powder Weigh 11 g of TiO2 into a clean container, then add 500 mL of deionized water and stir at 1000 rpm for 10 min to fully disperse the TiO2. Weigh 0.80 g of AgNO3 and pour it into the above deionized water, stirring at 1000 rpm for 10 min to fully dissolve it. Then, weigh 0.78 g of KI into a clean container, add 10 mL of deionized water, sonicate to dissolve, and pour into the above AgNO3 solution. React in the dark for 30 min. Filter and dry the resulting TiO2@AgI dispersion. Ball mill the sample for 20 min at 600 rpm with a ball-to-material ratio of 4.1:1. The particle size range of TiO2@AgI after ball milling is 120–550 nm.

[0067] S2: Preparation of silicone oil spinning solution Take a clean container and add 32.5 g of α,ω-vinyl polymethylphenylsiloxane (1000 cp), 4.8 g of α,ω-vinyl poly(methylphenylsiloxane-methylvinylsiloxane) (5000 cp) and 2.7 g of α,ω-dimethyl polymethylhydrosiloxane (0.75% hydrogen content) in sequence. Mix the silicone oil evenly at a stirring speed of 150 rpm to obtain the silicone oil spinning solution.

[0068] S3: Add TiO2@AgI to the silicone oil spinning solution 0.8 g (2% of the mass of the silicone oil spinning solution) of TiO2@AgI prepared in S1 was added to the silicone oil spinning solution prepared in S2, and the mixture was stirred at a stirring rate of 2000 rpm for 6 h to fully disperse TiO2@AgI in the silicone oil spinning solution.

[0069] S4: Prepolymer Add 0.1% (5000 ppm) of the inhibitor ethynylcyclohexanol (equivalent to 0.1% of the total mass of silicone oil) to the silicone oil spinning solution obtained in S3, and stir for 5 min to ensure that the inhibitor is evenly distributed in the spinning solution; then add 3000 ppm of platinum catalyst Karstedt and 0.1% (equivalent to 0.1% of the total mass of silicone oil) of dipinacol diboronate, control the system temperature at 25℃, and stir at 150 rpm for about 15 min to prepolymerize the spinning solution to a spinnable state, thus obtaining the spinning solution prepolymer.

[0070] S5: High-temperature air-induced cross-linking and curing into filaments After fully degassing the spinning solution prepolymer prepared by S4, it was added to the spinning equipment and injected into a 50 mL syringe, which was then clamped onto a constant pressure injection pump. The injection speed of the constant pressure injection pump was set to 0.65 mL / min. -1The actual heating temperature at the center of the heating sleeve was measured to be approximately 200℃~220℃. When the spinning solution prepolymer passed through the heating sleeve at a uniform speed, it underwent stretching and in-situ cross-linking and curing simultaneously, and was fully cured upon entering the rotating collection cage, resulting in a reversible thermochromic antibacterial silicone fiber product. The tensile strength of the silicone fiber prepared in this embodiment was measured to be 0.89 cN·tex using a dual-arm material testing machine. -1 .

[0071] Example 10: Referring to Example 9, the ball milling parameters in S1 were adjusted to 20 min for time, 200 rpm for rotation speed, and a ball-to-material ratio of 1.4:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 100 nm to 1.5 μm. The tensile strength of the organosilicon fiber prepared in this example was measured to be 0.44 cN·tex using a double-arm material testing machine. -1 .

[0072] Example 11: Referring to Example 9, the ball milling parameters in S1 were adjusted to 20 min for time, 400 rpm for speed, and a ball-to-material ratio of 2.7:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 100 nm to 950 nm. The tensile strength of the organosilicon fiber prepared in this example was 0.67 cN·tex, as tested using a double-arm material testing machine. -1 .

[0073] Example 12: Referring to Example 9, the ball milling parameters in S1 were adjusted to 40 min for time, 200 rpm for rotation speed, and a ball-to-material ratio of 3.3:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 140 nm to 950 nm. The tensile strength of the organosilicon fiber prepared in this example was 0.63 cN·tex, as tested using a double-arm material testing machine. -1 .

[0074] Example 13: Referring to Example 9, the ball milling parameters in S1 were adjusted to 40 min for time, 400 rpm for rotation speed, and a ball-to-material ratio of 3.0:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 120 nm to 700 nm. The tensile strength of the organosilicon fiber prepared in this example was 0.83 cN·tex, as tested using a double-arm material testing machine. -1 .

[0075] Example 14: Referring to Example 9, the ball milling parameters in S1 were adjusted to 40 min for time, 600 rpm for rotation speed, and a ball-to-material ratio of 1.9:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 100 nm to 750 nm. The tensile strength of the organosilicon fiber prepared in this example was 0.71 cN·tex, as tested using a double-arm material testing machine. -1 .

[0076] Example 15: Referring to Example 9, the ball milling parameters in S1 were adjusted to 60 min for time, 200 rpm for rotation speed, and a ball-to-material ratio of 3.6:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 120 nm to 650 nm. The tensile strength of the organosilicon fiber prepared in this example was 0.81 cN·tex, as tested using a double-arm material testing machine. -1 .

[0077] Example 16: Referring to Example 9, the ball milling parameters in S1 were adjusted to 60 min for time, 400 rpm for rotation speed, and a ball-to-material ratio of 2.5:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 120 nm to 630 nm. The tensile strength of the organosilicon fiber prepared in this example was 0.82 cN·tex, as tested using a double-arm material testing machine. -1 .

[0078] Example 17: Referring to Example 9, the ball milling parameters in S1 were adjusted to 60 min for time, 600 rpm for rotation speed, and a ball-to-material ratio of 2.2:1. All other conditions and operating steps were the same as in Example 9. After ball milling, the particle size range of TiO2@AgI was measured to be 100 nm to 630 nm. The tensile strength of the organosilicon fiber prepared in this example was measured to be 0.81 cN·tex using a double-arm material testing machine. -1 .

[0079] The tensile strength of the organosilicon fibers prepared in the above embodiments is as follows: Figure 12 As shown in (a), the silicone fiber obtained in Example 9 exhibits the best tensile strength, which is 0.89 cN·tex. -1 The tensile strength of the silicone fibers obtained in the other embodiments was lower than the above value. Combined with particle size distribution analysis, the particle distribution in the other embodiments was uneven, with some particles larger than 2.3 μm. Figure 12As shown in (c), the average diameter of the silicone fiber is approximately 300 μm. Larger particles occupy most of the fiber's cross-section, inevitably causing uneven distribution of molecular chains. This results in stress concentration on the larger particles under external force, leading to fiber breakage; in contrast, as shown in (c), the average diameter of the silicone fiber is approximately 300 μm. Figure 12 As shown in (b), the particle size distribution in Example 9 is more uniform, with the particle size mainly concentrated at 326 nm. In this case, the particles have less impact on the distribution of molecular chains within the fiber, and the fiber maintains satisfactory results even under external stretching. Furthermore, analysis reveals that the ball milling speed has the greatest impact on the particle size and distribution of TiO2@AgI, followed by the ball milling time. Conversely, the ball-to-material ratio has the least impact; the optimal ball milling process is as follows: time 60 min, speed 600 rpm, and ball-to-material ratio 4.1:1. Under this optimal scheme, the average strength of the silicone fiber reaches 0.90 cN·tex. -1 above.

[0080] This invention analyzes TiO2@AgI through the following embodiments. (11:1) The effect of the amount of additive on fiber properties.

[0081] Example 18: This embodiment provides a reversible thermochromic antibacterial silicone fiber, the preparation method of which includes the following steps: S1: Synthesis of TiO2@AgI powder Weigh 11 g of TiO2 into a clean container, then add 500 mL of deionized water and stir at 1000 rpm for 10 min to fully disperse the TiO2. Weigh 0.80 g of AgNO3 and pour it into the above deionized water, stirring at 1000 rpm for 10 min to fully dissolve it. Then, weigh 0.78 g of KI into a clean container, add 10 mL of deionized water, sonicate to dissolve, and pour into the above AgNO3 solution. React in the dark for 30 min. Filter and dry the resulting TiO2@AgI dispersion. Ball mill the sample for 60 min at 600 rpm with a ball-to-material ratio of 4.1:1.

[0082] S2: Preparation of silicone oil spinning solution Take a clean container and add 32.5 g of α,ω-vinyl polymethylphenylsiloxane (1000 cp), 4.8 g of α,ω-vinyl poly(methylphenylsiloxane-methylvinylsiloxane) (5000 cp) and 2.7 g of α,ω-dimethyl polymethylhydrosiloxane (0.75% hydrogen content) in sequence. Mix the silicone oil evenly at a stirring speed of 150 rpm to obtain the silicone oil spinning solution.

[0083] S3: Add TiO2@AgI to the silicone oil spinning solution 0.8 g (2% of the mass of the silicone oil spinning solution) of TiO2@AgI prepared in S1 was added to the silicone oil spinning solution prepared in S2, and the mixture was stirred at a stirring rate of 2000 rpm for 6 h to fully disperse TiO2@AgI in the silicone oil spinning solution.

[0084] S4: Prepolymer Add 0.1% (5000 ppm) of the inhibitor ethynylcyclohexanol (equivalent to 0.1% of the total mass of silicone oil) to the silicone oil spinning solution obtained in S3, and stir for 5 min to ensure that the inhibitor is evenly distributed in the spinning solution; then add 3000 ppm of platinum catalyst Karstedt and 0.1% (equivalent to 0.1% of the total mass of silicone oil) of dipinacol diboronate, control the system temperature at 25℃, and stir at 150 rpm for about 15 min to prepolymerize the spinning solution to a spinnable state, thus obtaining the spinning solution prepolymer.

[0085] S5: High-temperature air-induced cross-linking and curing into filaments After fully degassing the spinning solution prepolymer prepared by S4, it was added to the spinning equipment and injected into a 50 mL syringe, which was then clamped onto a constant pressure injection pump. The injection speed of the constant pressure injection pump was set to 0.65 mL / min. -1 The actual heating temperature at the center of the heating sleeve was measured to be approximately 200℃~220℃. When the spinning solution prepolymer passes through the heating sleeve at a uniform speed, it undergoes stretching and in-situ cross-linking and curing, and is fully cured upon entering the rotating collection cage, resulting in a reversible thermochromic antibacterial silicone fiber product, codenamed TiO2@AgI. (11:1) @SiF-2-1. The tensile strength of the organosilicon fiber prepared in this embodiment was 0.92 cN·tex, as tested using a double-arm material testing machine. -1 .

[0086] The reversible thermochromic antibacterial organosilicon fiber TiO2@AgI prepared in Example 18 (11:1) @SiF-2-1 was quickly placed on a heating platform at 170°C; its low thermal conductivity caused its temperature to rise rapidly. Figure 13 The macroscopic color change and infrared thermography of this process are shown in the image. Initially, the fiber is white. After 9 seconds of heating, the fiber temperature reaches 125°C, indicating a rapid heating rate; at this point, the fiber color remains unchanged. After 13 seconds of heating, the fiber temperature reaches 145°C and turns slightly yellow, consistent with previously measured color change temperatures. After another 21 seconds of heating, the fiber turns completely bright yellow. The fiber reaches its color change temperature from room temperature in approximately 9 to 13 seconds, demonstrating a rapid response to color change when in contact with high-temperature equipment.

[0087] The reversible thermochromic antibacterial organosilicon fiber TiO2@AgI prepared in this embodiment (11:1) The color-changing sensitivity of @SiF-2-1 is as follows Figure 14 As shown in the infrared thermogram, when the fiber temperature is below 134 ℃, it appears milky white; when the temperature reaches 135 ℃-136 ℃, it gradually turns bright yellow. In three tests, the error in the color change temperature remained within 1 ℃, indicating that TiO2@AgI... (11:1) @SiF-2-1 has color-changing sensitivity, enabling it to react quickly and accurately to abnormal heat sources.

[0088] Example 19: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 0.2 g (0.5% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-0.5. The tensile strength of the organosilicon fiber prepared in this embodiment was 1.03 cN·tex, as tested using a double-arm material testing machine. -1 The color difference before and after thermochromic change was 8.68, and the antibacterial rate was 90.89%.

[0089] Example 20: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 0.4 g (1.0% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-1. The tensile strength of the organosilicon fiber prepared in this embodiment was 1.01 cN·tex, as tested using a dual-arm material testing machine. -1 The color difference before and after thermochromic change was 14.36, and the antibacterial rate was 94.36%.

[0090] Example 21: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 0.6 g (1.5% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-1.5. The tensile strength of the organosilicon fiber prepared in this embodiment was 0.99 cN·tex, as tested using a bi-arm material testing machine. -1 The color difference before and after thermochromic change was 18.28, and the antibacterial rate was 98.28%.

[0091] Example 22: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 1.0 g (2.5% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI.(11:1) @SiF-2.5. The tensile strength of the silicone fiber prepared in this embodiment was 0.88 cN·tex, as determined by a bi-arm material testing machine. -1 The color difference before and after thermochromic change is 24.98, and the antibacterial rate is 99.99%.

[0092] Example 23: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 1.2 g (3.0% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-3. The tensile strength of the silicone fiber prepared in this embodiment was 0.83 cN·tex, as determined by a bi-arm material testing machine. -1 The color difference before and after thermochromic change is 25.77, and the antibacterial rate is 99.99%.

[0093] Example 24: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 1.4 g (3.5% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-3.5. The tensile strength of the silicone fiber prepared in this embodiment was 0.82 cN·tex, as determined by a bi-arm material testing machine. -1 The color difference before and after thermochromic change is 23.34, and the antibacterial rate is 99.99%.

[0094] Example 25: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 1.6 g (4.0% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-4. The tensile strength of the silicone fiber prepared in this embodiment was 0.74 cN·tex, as determined by a bi-arm material testing machine. -1 The color difference before and after thermochromic change is 23.36, and the antibacterial rate is 99.99%.

[0095] Example 26: Referring to Example 18, the amount of TiO2@AgI added in S3 was adjusted to 1.8 g (4.5% of the spinning solution mass), and other conditions and operating steps were the same as in Example 18. The sample code was TiO2@AgI. (11:1) @SiF-4.5. The tensile strength of the silicone fiber prepared in this embodiment was 0.72 cN·tex, as determined by a bi-arm material testing machine. -1The color difference before and after thermochromic change is 24.53, and the antibacterial rate is 99.99%.

[0096] from Figure 15 (a) Analysis shows that as TiO2@AgI (11:1) With increasing addition amount, the number of particles per unit area of ​​fiber cross-section increases, and the molecular chain distribution decreases, thereby reducing the tensile strength of the fiber. Linear fitting results show a negative linear correlation between addition amount and tensile strength (R0). 2 =0.9661), and most of the measurements were within the 95% confidence range, indicating that the test results were accurate. Figure 15 (b) shows the addition of 2 wt% TiO2@AgI (11:1) The stress-strain curve of the post-fiber shows that before the elongation reaches 25 mm, only a small portion of the organosilicon macromolecules are stretched and oriented under external force. During this period, the tensile strength of the fiber does not change significantly, and the initial modulus of the fiber is low. When the fiber is stretched beyond 25 mm, due to the limitation of cross-linking, most of the molecular chains are not easily stretched and instead share the load. Therefore, the modulus of the fiber increases sharply, and the fiber breaks under external force. Calculations show that TiO2@AgI... (11:1) The average tensile strength of @SiF-2-1 is approximately 0.92 cN·tex. -1 (Approximately 9.89 MPa ~ 11.33 MPa), fracture work is 11.53 N·mm. Figure 15 (c) shows TiO2@AgI (11:1) The cyclic tensile test results of @SiF-2 with a tensile elongation of 100% showed that after 150 tensile cycles, the tensile strength of the fiber remained stable without stress relaxation. This indicates that TiO2@AgI (11:1) @SiF-2-1 exhibits excellent resilience and fatigue resistance, making it suitable for use in extreme environments.

[0097] In addition, TiO2@AgI (11:1) The relative amount added will affect the color intensity after the fiber changes color. Figure 16 (a) shows different TiO2@AgI (11:1) A comparison of the fiber color change before and after the change in TiO2@AgI content; the color difference value varies with the change in TiO2@AgI content. (11:1) The content increases with the increase; and Figure 16 (b) shows that when 2 wt% TiO2@AgI is added... (11:1) At that time, TiO2@AgI (11:1) @SiF-2-1 is white at 20℃ and bright yellow at 150℃, with a color difference of 25.72. When 3 wt% TiO2@AgI is added... (11:1)At this point, the color difference reaches its maximum value (25.77), which is very small compared to the value at 2 wt%. This is because TiO2@AgI (11:1) The addition of TiO2@AgI to the fiber surface is already close to saturation; further increasing the amount will not significantly improve the performance. (11:1) Color difference value of @SiF-2-1.

[0098] In summary, this invention successfully prepared reversible thermochromic antibacterial organosilicon fibers using divinyl-terminated phenyl silicone oil (terminated vinyl silicone oil) and end-side polyvinylphenyl silicone oil (side-side vinyl silicone oil) as the main fiber structure, hydrogen-containing silicone oil (hydrogen-based silicone oil) as the crosslinking agent, and TiO2@AgI as the inorganic thermochromic antibacterial powder. The aim was to prepare a functional fiber material possessing high-temperature color change, antibacterial non-toxicity, and excellent mechanical properties. Instrumental characterization and various performance tests revealed that the organosilicon fibers have the following characteristics: First, SEM and ultra-depth-of-field 3D microscopy revealed that TSiF has a smooth longitudinal surface and uniform cross-sectional thickness. Combined with EDS analysis, it was found that TSiF is mainly composed of six elements: Si, O, C, Ti, Ag, and I; these findings indicate the successful preparation of reversible thermochromic antibacterial silicone fibers. The discoloration and antibacterial properties of TiO2@AgI can be adjusted by changing the mass ratio of TiO2 to AgI. Studies have shown that when the mass ratio of TiO2 to AgI is 11:1, the discoloration and antibacterial properties of TiO2@AgI are optimal. (11:1) @SiF-2 achieves the best overall performance in terms of color-changing properties and antibacterial efficacy. The measured values ​​for TiO2@AgI... (11:1) The color difference of SiF-2 before and after thermochromic change was 25.72, and the antibacterial rate was as high as 99.99%. Different concentrations of TiO2@AgI... (11:1) After co-culturing the @SiF-2 extract with L929 cells for 12 h, the cell viability remained above 98%.

[0099] Secondly, the prepared TiO2@AgI was ball-milled to investigate the effect of TiO2@AgI particle size and distribution on the mechanical properties of the fiber. The addition amount was set to 2% of the spinning solution mass. The results showed that, under fixed parameters, when the ball milling time was 20 min, the rotation speed was 600 rpm, and the ball-to-material ratio was 4.1:1, the TiO2@AgI particle size distribution was uniform, and the tensile strength of the prepared fiber reached its optimal level of approximately 0.89 cN·tex. -1 The optimal ball milling parameters were determined to be 60 min milling time, 600 rpm milling speed, and a ball-to-material ratio of 4.1:1. Under these conditions, the tensile strength of the prepared fibers was further improved to approximately 0.92 cN·tex. -1(Approximately 9.89 MPa ~ 11.33 MPa).

[0100] Finally, the combined effects of TiO2@AgI addition amount on fiber tensile strength, color change properties, and antibacterial properties were studied. The TiO2@AgI addition amount ranged from 0.5% to 4.5% of the spinning solution mass. When the addition amount was 2.0% of the spinning solution mass, the prepared TiO2@AgI... (11:1) @SiF-2 has a color difference close to its maximum value and can change color quickly when in contact with a high-temperature heat source, as well as excellent color change sensitivity. The antibacterial rate reaches its maximum value, and the tensile strength is also high. After 150 cycles of 100% stretching, the tensile strength remains unchanged.

[0101] The reversible thermochromic antibacterial silicone fiber prepared by this invention not only has high-temperature reversible thermochromic properties and fast response, but also has antibacterial and non-toxic characteristics, as well as excellent tensile strength. Moreover, the preparation process is simpler and lower in cost, making it suitable for industrial production.

[0102] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and principles of the described embodiments, and these modifications and variations should also be considered within the scope of protection of the present invention.

Claims

1. A reversible thermochromic antibacterial organosilicon fiber, characterized in that, The raw materials for the organosilicon fiber include silicone oil spinning solution, TiO2@AgI powder, catalyst, inhibitor, and curing accelerator; the silicone oil spinning solution includes vinyl silicone oil and hydrogen-based silicone oil in a mass ratio of 1:(0.8~1.4), the vinyl silicone oil includes terminal vinyl silicone oil and side vinyl silicone oil, and the amount of side vinyl silicone oil added is 14 wt%~16 wt%; the amount of TiO2@AgI powder added is 0.5 wt%~4.5 wt% of the total amount of silicone oil spinning solution; the amount of catalyst, inhibitor, and curing accelerator added is 0.1 wt%~1 wt% of the total amount of silicone oil spinning solution. The inhibitor is acetylenol, 2-methyl-3-butanol-2-ol, or butynediol, and the curing accelerator is borate ester. In the TiO2@AgI powder, AgI is dispersed and loaded in nano-form on the TiO2 substrate, and the mass ratio of AgI to TiO2 is 1:(1~50). The particle size of TiO2@AgI is 100nm~5μm.

2. The reversible thermochromic antibacterial silicone fiber according to claim 1, characterized in that, The mass ratio of AgI to TiO2 in the TiO2@AgI is 1:(10~11), and the particle size of the TiO2@AgI is 100 nm~500 nm.

3. The reversible thermochromic antibacterial silicone fiber according to claim 2, characterized in that, The TiO2 is rutile phase, anatase phase, or a mixture of both phases.

4. The reversible thermochromic antibacterial silicone fiber according to any one of claims 1 to 3, characterized in that, The preparation method of the TiO2@AgI powder includes: TiO2@AgI powder was prepared by mixing TiO2, KI and AgNO3 in deionized water and using a dissolution-precipitation method. The mass ratio of TiO2, KI and AgNO3 is (5~20):0.78:0.8, and the reaction time of the dissolution-precipitation method is 5 min~120 min.

5. The reversible thermochromic antibacterial silicone fiber according to claim 4, characterized in that, The mass ratio of TiO2, KI and AgNO3 is (10~15):0.78:0.8, and the reaction time is 5min~60min.

6. The reversible thermochromic antibacterial silicone fiber according to claim 4, characterized in that, Also includes: After the dissolution-precipitation reaction is completed, the obtained product is ball-milled using a ball milling device.

7. The reversible thermochromic antibacterial silicone fiber according to claim 6, characterized in that, The ball milling parameters include: a ball milling time of 20 min to 60 min, a rotation speed of 200 rpm to 600 rpm, and a ball-to-material ratio of (1.4 to 4.1):

1.

8. The reversible thermochromic antibacterial organosilicon fiber according to claim 1, characterized in that, The mass ratio of the vinyl silicone oil to the hydrogen-based silicone oil is 1:(1.1~1.2), and the amount of TiO2@AgI added is 1 wt%~5 wt% of the total amount of silicone oil.

9. A method for preparing the reversible thermochromic antibacterial organosilicon fiber according to claim 1, characterized in that, include: TiO2@AgI powder material was prepared by mixing TiO2, KI and AgNO3 in deionized water and using a dissolution-precipitation method. Vinyl silicone oil and hydrogen-based silicone oil are mixed evenly in a certain proportion to prepare a silicone oil spinning solution; The TiO2@AgI powder material was added to the silicone oil spinning solution and dispersed evenly. A catalyst, an inhibitor, and a curing accelerator were added to a silicone oil spinning solution containing TiO2@AgI powder, and the mixture was stirred to obtain a spinning solution prepolymer. The above-mentioned spinning solution prepolymer is added to the spinning equipment, and cross-linking and curing are induced by air heating, and then spun into fibers.

10. The method for preparing reversible thermochromic antibacterial organosilicon fiber according to claim 9, characterized in that, Also includes: After the dissolution-precipitation reaction is completed, the obtained product is ball-milled using a ball milling device.

11. The application of the reversible thermochromic antibacterial silicone fiber according to claim 1 in the preparation of reversible thermochromic materials.

12. The application of the reversible thermochromic antibacterial silicone fiber according to claim 1 in the preparation of antibacterial materials.

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