Fabric with cool feeling and antibacterial function and preparation method thereof

Abstract

The application discloses a fabric with cool feeling and antibacterial function and a preparation method thereof, and belongs to the field of functional textile preparation. The preparation method of the antibacterial multifunctional material comprises the following steps: S1, dispersing polystyrene microspheres in a buffer solution containing dopamine and boron nitride nanosheets to obtain a dispersion liquid, and treating the dispersion liquid by oscillation to coat the surfaces of the polystyrene microspheres with polydopamine and boron nitride nanosheets, so as to form a precursor; S2, mixing the precursor with a metal salt, and performing hydrothermal treatment under alkaline conditions, and then drying to obtain a composite material loaded with layered double hydroxide; and S3, calcining the composite material under a protective atmosphere to decompose organic matters and form a hollow structure. By using the antibacterial multifunctional material provided by the application, the fabric is treated through finishing, so that the fabric has good antibacterial performance and also has the multifunctional experience of cool wearing and comfort.

Description

Technical Field

[0001] This invention belongs to the field of functional textile preparation, and relates to a method for preparing an antibacterial multifunctional material, a fabric with cooling and antibacterial functions, and a method for preparing the same. Background Technology

[0002] With the significant improvement in people's quality of life and the increasing awareness of health and safety, the importance of antibacterial textiles has become increasingly prominent. They play a crucial role in inhibiting the growth of harmful microorganisms and protecting human health and hygiene. Meanwhile, the application areas of antibacterial fabrics are continuously expanding, from initial medical protective and hygiene products to home textiles, vehicle interiors, public space facilities, and personal care products. Therefore, how to effectively achieve excellent antibacterial properties in textile fabrics has become a core issue of concern in the industry.

[0003] Currently, methods for imparting antibacterial properties to fabrics include melt spinning, finishing, and lamination. Among these, finishing, a widely used method, introduces antibacterial agents onto the fabric surface or within the fibers through chemical treatment or coating without altering the basic textile process, thereby improving the fabric's antibacterial properties. This treatment method offers advantages such as high operational flexibility, wide applicability, and relatively low cost. Furthermore, the type and dosage of antibacterial agents can be adjusted according to specific application requirements to achieve a more ideal antibacterial effect. In addition, antibacterial finishing treatments can provide extra functional protection while maintaining the fabric's original style and comfort, making them particularly suitable for products with special requirements for the fabric's intended use.

[0004] In the prior art, Chinese patent document CN 206814953 U discloses a silk-linen silver ion antibacterial fabric. It is woven from silver ion acrylic yarn and a blend of silk / Apocynum venetum yarn, thus achieving antibacterial, bactericidal, and UV-protective functions. However, since silver is a precious metal, silver ions are lost during use, significantly reducing its durability and making it unsuitable for mass production and large-scale application. Summary of the Invention

[0005] To address the shortcomings of the existing technology, the purpose of this invention is to provide a method for preparing an antibacterial multifunctional material, a fabric with cooling and antibacterial functions, and a method for preparing the same. By using the antibacterial multifunctional material provided by this invention and performing post-treatment on the fabric, the fabric can have good antibacterial properties while also providing a cool and comfortable multifunctional wearing experience.

[0006] This invention provides a method for preparing an antibacterial multifunctional material, comprising the following steps:

[0007] S1. Polystyrene microspheres are dispersed in a buffer solution containing dopamine and boron nitride nanosheets to obtain a dispersion. The dispersion is then subjected to shaking treatment to coat the surface of the polystyrene microspheres with polydopamine and boron nitride nanosheets to form a precursor.

[0008] S2. The precursor is mixed with a metal salt and subjected to hydrothermal treatment under alkaline conditions. After drying, a composite material loaded with layered bimetallic hydroxides is obtained. The metal salt includes soluble divalent metal salts and soluble trivalent metal salts.

[0009] S3. Under a protective atmosphere, the composite material is calcined to decompose the organic matter and form a hollow structure, thereby obtaining an antibacterial multifunctional material.

[0010] To achieve the above objectives, the embodiments of the present invention employ the following technical solution: First, an antibacterial multifunctional material is prepared, specifically polystyrene microspheres (PS microspheres). The obtained PS microspheres, layered bimetallic hydroxides, and boron nitride (BN) are combined, so that boron nitride and layered bimetallic hydroxides are coated on the PS microspheres (this process corresponds to step S1 forming the precursor and step S2 obtaining the composite material). Then, the microspheres are decomposed by calcination, leaving hollow boron nitride and layered bimetallic oxides, thus obtaining the final product (this process corresponds to step S3). Afterward, the obtained antibacterial multifunctional material is applied to fabrics through finishing processes.

[0011] As a preferred embodiment of the above technical solution, in step S1, the polystyrene microspheres are prepared by the following operation: polyvinylpyrrolidone (PVP), 2,2′-azobisisobutylamidine dihydrochloride (AIBA) and styrene monomer are mixed in water, and then heated to react, and polystyrene microspheres (PS microspheres) are obtained by separation.

[0012] Further, in step S1, the concentration of PVP is 75~600µM, the concentration of AIBA is 1.2~38mM, and the concentration of styrene monomer can be 0.9~1mM, for example, 0.96mM. The water is usually deionized water, and the preferred temperature for the heating reaction is 60~80℃, further raised to 70℃ and held at that temperature for 24 hours.

[0013] As a preferred embodiment of the above technical solution, in step S1, the concentration of polystyrene microspheres in the dispersion is 1-3 g / L; the concentration of dopamine (DA) is 0.2-5 g / L, further 0.5-3 g / L; and the concentration of BN nanosheets is 7-10 g / L. The buffer solution is a Tris buffer solution or a carbonate buffer solution. In this embodiment of the invention, the dispersion is shaken and then dried in an oven to obtain a precursor for PS microspheres coated with polydopamine and BN nanosheets. This embodiment of the invention utilizes the good lubricity and thermal conductivity of boron nitride (BN), which is beneficial for reducing friction between fabric fibers and improving wearing comfort. Generally, the surface of boron nitride is rich in nitrogen, which can capture metal ions, facilitating the growth of layered bimetallic structures. Furthermore, the diameter of the PS microspheres can be controlled between 200-800 nm, which is beneficial for improving solar reflectivity through Mie scattering.

[0014] In this embodiment of the invention, a mixed solution of divalent and trivalent metal salts and an alkaline solution (referred to as alkaline solution) can be prepared, and then the composite material is obtained by hydrothermal treatment and drying.

[0015] As a preferred embodiment of the above technical solution, in step S2, the divalent metal ion in the soluble divalent metal salt is Cu. 2+ Ni 2+ Zn 2+ Fe 2+ Mg 2+ One or two of the following; the trivalent metal ion in the soluble trivalent metal salt is Ti. 3+ Fe 3+ Al 3+ Ni 3+ Cr 3+ One or two of the following; the anions in the soluble divalent metal salt and the soluble trivalent metal salt are Cl... - NO3 - CO3 2- SO4 2- One of them. Specifically, the metal salt may be a zinc sulfate, hydrochloride, or nitrate; copper sulfate or copper nitrate; ferric chloride, ferric nitrate, or ferric sulfate; etc.

[0016] As a preferred embodiment of the above technical solution, in step S2, the alkaline conditions are achieved by adding sodium hydroxide and / or ammonia, i.e., adding the prepared alkaline solution to the mixture, or directly adding an alkaline solid; the amount of the precursor added is 1~5 g / L; the temperature of the hydrothermal treatment is 95~110℃, and the time is 6~24 h.

[0017] As a preferred embodiment of the above technical solution, in step S2, the total concentration of the soluble divalent metal salt and the soluble trivalent metal salt is 0.05~0.5mol / L, the molar ratio of the soluble divalent metal salt to the soluble trivalent metal salt is 0.5~5:1, and the molar ratio of the total amount of the soluble divalent metal salt and the soluble trivalent metal salt to the alkaline substance is 1:1~10.

[0018] After obtaining the composite material loaded with layered metal hydroxide in the embodiments of the present invention, it can be placed in a tube furnace filled with argon for calcination to obtain a material with hollow carbon microspheres supporting boron nitride and layered bimetallic oxide, wherein the size of the hollow spheres can be controlled between 200-800 nm; that is, the final product - an antibacterial multifunctional material.

[0019] As a preferred embodiment of the above technical solution, step S3, calcining the composite material includes: heating to 350-450°C at a rate of 1-5°C / min and holding for 3-5 hours to slowly decompose the PS microsphere template and form a hollow structure; then heating to 550-650°C at a rate of 1-3°C / min and holding for 2-4 hours to obtain the final product. For example, first heating to 350-450°C at a rate of 5°C / min and holding for 4 hours, then heating to 550-650°C at a rate of 2°C / min and holding for 3 hours to obtain the final product.

[0020] This invention utilizes layered bimetallic hydroxide (LDH) as the primary antibacterial agent. Its unique layered structure and synergistic multi-mechanism action endow it with excellent antibacterial properties: its positively charged layers can adsorb and physically penetrate bacterial cells, while simultaneously creating an alkaline microenvironment through hydrolysis and disrupting cell membranes; more importantly, the antibacterial metal ions in the layers or the active ingredients loaded between the layers can be slowly released, providing long-term interference with bacterial metabolism and catalyzing the production of reactive oxygen species (ROS), thus achieving oxidative damage to microbial DNA and proteins. This synergistic effect of "physical destruction + chemical attack + slow-release sterilization" gives it the advantages of high efficiency, long-lasting effect, and low toxicity in antibacterial treatment.

[0021] This invention utilizes LDH and BN nanosheets loaded onto polydopamine (PDA) modified PS microspheres, followed by calcination to prepare a hollow composite material. This composite material enhances light scattering efficiency, effectively reflecting sunlight. Combined with BN, it provides superior cooling properties. This method is simple to operate, uses mild reaction conditions, and results in fabrics with good antibacterial properties, excellent durability, and comfortable wear.

[0022] This invention provides a fabric with cooling and antibacterial functions, formed by finishing a fabric. The finishing process uses a working solution containing an adhesive and a functional finishing agent, wherein the functional finishing agent is an antibacterial multifunctional material obtained by the preparation method described above.

[0023] Accordingly, the present invention provides a method for preparing a fabric with cooling and antibacterial functions as described above, comprising:

[0024] The functional finishing agent is dispersed in a solution containing an adhesive to obtain a suspension; the functional finishing agent is an antibacterial multifunctional material prepared by the method described above.

[0025] The fabric is placed in the suspension, subjected to agitation, and then dried to obtain the fabric with cooling and antibacterial functions.

[0026] This invention provides a mixture of antibacterial multifunctional materials, preferably utilizing the adhesive properties of water-based acrylic acid to firmly adhere the antibacterial multifunctional material to the surface of the fabric to be treated. This method combines the thermal conductivity of boron nitride and the antibacterial properties of layered bimetallic oxides with the adhesive properties of water-based acrylic acid, forming a multifunctional protective layer on the fabric surface. This ensures the fabric's antibacterial properties, while the excellent surface area of ​​the spherical boron nitride effectively improves its thermal conductivity. Furthermore, the hollow structure formed enhances light scattering efficiency, effectively reflecting sunlight and making the treated fabric cooler and more comfortable to wear.

[0027] As a preferred embodiment of the above technical solution, the adhesive is water-based acrylic acid, and commercially available products are acceptable; the fabric is polyester and / or cotton fiber fabric. Furthermore, the embodiments of the present invention do not impose special limitations on the basic textile process parameters of the fabric, and this process is applicable to different fabrics.

[0028] As a preferred embodiment of the above technical solution, the concentrations of the functional finishing agent and the adhesive in the suspension are 1~3g / L, respectively; the fabric is a clean fabric that has been soaked and washed with water and ethanol in sequence and then dried; the temperature of the oscillation treatment is 20~50℃, the oscillation speed is 100-300r / min, and the time is 6~24h.

[0029] The specific production process of the fabric with cooling and antibacterial functions provided in this invention embodiment is as follows:

[0030] (1) Polyvinylpyrrolidone (PVP) and azobisisobutyramidine hydrochloride (AIBA) were dissolved in deionized water in a three-necked flask, styrene was added, the reaction temperature was gradually increased to 70°C and kept at that temperature for 24 hours, and finally the mixture was cooled to room temperature. The synthesized PS particles were filtered and washed to remove residual styrene and PVP. The obtained sample was dried in a vacuum oven to obtain PS microspheres.

[0031] (2) The PS microspheres obtained in step (1) were dispersed in a buffer solution containing dopamine (DA) and boron nitride (BN) nanosheets, shaken (6~24h, 25℃) and then dried in an oven to obtain a precursor of PS coated with polydopamine (PDA) and BN nanosheets, denoted as PS@PDA-BN;

[0032] (3) Prepare a mixed solution containing soluble divalent metal salt, a mixed solution containing soluble trivalent metal salt, and an alkaline solution. Add the PS@PDA-BN precursor from step (2) to the mixed solution of metal salts for dispersion. Then add the alkaline solution to the mixture. The mixture is subjected to hydrothermal treatment and vacuum drying to obtain a composite material loaded with layered double metal hydroxide (LDH), denoted as PS@PDA-BN-LDH.

[0033] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection to obtain a carbon microsphere-supported boron nitride and layered bimetallic oxide material with a hollow structure, denoted as HC@BN-LDO;

[0034] (5) Disperse the product obtained in step (4) in a solution containing adhesive to form a stable suspension, place the clean fabric in it, shake it, and then dry it in an oven to obtain the fabric.

[0035] This invention utilizes PS microspheres as a template to prepare composite boron nitride and layered bimetallic hydroxides, significantly increasing their surface area and enhancing their cooling and antibacterial effects. Furthermore, the prepared hollow structure improves light scattering efficiency, effectively reflecting sunlight and making the treated fabric cooler and more comfortable to wear.

[0036] The production method of this invention is relatively simple and low in cost. By changing the amount of adhesive added, the type of buffer solution, and the time, the thickness and uniformity of the protective layer adhering to the surface of the fabric fibers can be controlled to prevent the protective layer from blocking the gaps in the fabric, thereby maintaining the breathability of the fabric. Detailed Implementation

[0037] The technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0038] To better understand the technical content of this invention, specific embodiments are provided below to further illustrate the invention. The substances used in these embodiments are commercially available; the PVP has a molecular weight of 55,000; and the boron nitride nanosheets have a size of 200-500 nm.

[0039] Example 1

[0040] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0041] (1) Dissolve 75µM PVP and 38mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0042] (2) The 1 g / L PS microspheres obtained in step (1) were dispersed in 2 g / L Tris buffer containing 0.2 g / L dopamine and 7 g / L boron nitride nanosheets, shaken for 12 h, at 25 °C, the same as in the following examples, and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the PS surface;

[0043] (3) Dissolve 0.25g CuSO4, 0.7g ZnSO4, and 0.4g Al2(SO4)3 in 50mL of deionized water. Add the 2g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion. Then add 5mL of 20% ammonia water to the mixed solution and dissolve it completely. Then transfer it to a hydrothermal reactor and react at 100℃ for 6h. Dry it under vacuum to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH).

[0044] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 350°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 550°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0045] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 1 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 100 r / min. After 6 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0046] Example 2

[0047] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0048] (1) Dissolve 150µM PVP and 1.2mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0049] (2) The 1 g / L PS microspheres obtained in step (1) were dispersed in 2 g / L Tris buffer containing 0.2 g / L dopamine and 7 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the PS surface.

[0050] (3) Dissolve 1.05g Zn(NO3)2 and 0.4g Al(NO3)3 in 50mL of deionized water, add 2g / LPS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion, then add 5mL of 20% ammonia water to the mixed solution, dissolve it completely, then transfer it to a hydrothermal reactor and react at 100℃ for 6h, and vacuum dry to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH);

[0051] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 400°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 600°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0052] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 1 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 100 r / min. After 6 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0053] Example 3

[0054] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0055] (1) Dissolve 200µM PVP and 8mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0056] (2) The 1 g / L PS microspheres obtained in step (1) were dispersed in 2 g / L Tris buffer containing 1 g / L dopamine and 7 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the surface of PS.

[0057] (3) Dissolve 1g ZnCl2 and 0.3g FeCl3 in 50mL of deionized water, add the 1g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion, then add 5mL of 20% ammonia water to the mixed solution, dissolve it completely, then transfer it to a hydrothermal reactor and react at 100℃ for 6h, and vacuum dry to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH);

[0058] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 400°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 600°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0059] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 1 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 100 r / min. After 6 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0060] Example 4

[0061] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0062] (1) Dissolve 250µM PVP and 12mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0063] (2) The 1 g / L PS microspheres obtained in step (1) were dispersed in 2 g / L Tris buffer containing 1 g / L dopamine and 7 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the surface of PS.

[0064] (3) Dissolve 1g Cu(NO3)2, 1.1g Mg(NO3)2 and 0.8g Fe(NO3)3 in 50mL of deionized water. Add the 4g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion. Then add 5mL of 20% ammonia water to the mixed solution and dissolve it completely. Then transfer it to a hydrothermal reactor and react at 110℃ for 12h. Dry it under vacuum to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH).

[0065] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 400°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 600°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0066] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 2 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 100 r / min. After 6 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0067] Example 5

[0068] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0069] (1) Dissolve 300µM PVP and 18mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0070] (2) The 1 g / L PS microspheres obtained in step (1) were dispersed in 2 g / L Tris buffer containing 1 g / L dopamine and 9 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the PS surface.

[0071] (3) Dissolve 0.5g CuSO4 and 0.375g Fe2(SO4)3 in 50mL of deionized water, add 5g / LPS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion, then add 5mL of 20% ammonia water to the mixed solution, dissolve it completely, then transfer it to a hydrothermal reactor and react at 110℃ for 12h, and vacuum dry to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH);

[0072] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 450°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 600°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0073] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 2 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 200 r / min. After 12 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0074] Example 6

[0075] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0076] (1) Dissolve 360µM PVP and 23mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0077] (2) The 3 g / L PS microspheres obtained in step (1) were dispersed in 1 g / L phosphate buffer containing 5 g / L dopamine and 10 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the PS surface.

[0078] (3) Dissolve 0.4g CuSO4 and 0.1g Cr2(SO4)3 in 50mL of deionized water, add the 3g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion, then add 1.8g sodium hydroxide to the mixed solution and dissolve it completely. Then transfer it to a hydrothermal reactor and react at 110℃ for 24h. After vacuum drying, PS@PDA-BN-LDH material with layered bimetallic hydroxide (LDH) is obtained.

[0079] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 450°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 650°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0080] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 2 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 50°C and a shaking speed of 300 r / min. After 12 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0081] Example 7

[0082] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0083] (1) Dissolve 400µM PVP and 26mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0084] (2) The 3 g / L PS microspheres obtained in step (1) were dispersed in 1 g / L phosphate buffer containing 4 g / L dopamine and 9 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the PS surface.

[0085] (3) Dissolve 0.8g ZnCl2, 0.4g FeCl3 and 0.25g AlCl3 in 50mL of deionized water. Add the 2g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion. Then add 1.8g sodium hydroxide to the mixed solution and dissolve it completely. Then transfer it to a hydrothermal reactor and react at 110℃ for 24h. Dry it under vacuum to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH).

[0086] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 450°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 650°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0087] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 2 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 50°C and a shaking speed of 250 r / min. After 24 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0088] Example 8

[0089] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0090] (1) Dissolve 460µM PVP and 30mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0091] (2) The 3 g / L PS microspheres obtained in step (1) were dispersed in 1 g / L phosphate buffer containing 1 g / L dopamine and 7 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the surface of PS.

[0092] (3) Dissolve 0.25g Zn(NO3)2, 0.7g Mg(NO3)2, and 0.4g Fe(NO3)3 in 50mL of deionized water. Add the 4g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion. Then add 1.8g sodium hydroxide to the mixed solution and dissolve it completely. Transfer the solution to a hydrothermal reactor and react at 110℃ for 24h. Dry under vacuum to obtain PS@PDA-BN-LDH material supported on layered bimetallic hydroxide (LDH).

[0093] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 400°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 600°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0094] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 2 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 50°C and a shaking speed of 250 r / min. After 24 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0095] Example 9

[0096] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0097] (1) Dissolve 500µM PVP and 33mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0098] (2) The 3 g / L PS microspheres obtained in step (1) were dispersed in 1 g / L phosphate buffer containing 0.5 g / L dopamine and 7 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the PS surface.

[0099] (3) Dissolve 1g CuSO4 and 0.6g Fe(SO4)2 in 50mL of deionized water, add the 2g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion, then add 1.8g sodium hydroxide to the mixed solution and dissolve it completely. Then transfer it to a hydrothermal reactor and react at 110℃ for 24h. After vacuum drying, PS@PDA-BN-LDH material loaded with layered bimetallic hydroxide (LDH) is obtained.

[0100] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 350°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 550°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0101] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 2 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 50°C and a shaking speed of 250 r / min. After 24 h, the fabric is dried in an oven to obtain the fabric with cooling and antibacterial functions.

[0102] Example 10

[0103] A fabric with cooling and antibacterial functions and a method for preparing the same, the method comprising the following steps:

[0104] (1) Dissolve 600µM PVP and 38mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0105] (2) The 1 g / L PS microspheres obtained in step (1) were dispersed in 1 g / L phosphate buffer containing 3 g / L dopamine and 5 g / L boron nitride nanosheets, shaken and then dried in an oven to obtain the precursor PS@PDA-BN coated with PDA and BN nanosheets on the surface of PS.

[0106] (3) Dissolve 1.1g ZnSO4 and 0.5g Ti2(SO4)3 in 50mL of deionized water, add the 2g / L PS@PDA-BN precursor from step (2) to the metal salt mixed solution for dispersion, then add 1.8g sodium hydroxide to the mixed solution and dissolve it completely. Then transfer it to a hydrothermal reactor and react at 110℃ for 24h. After vacuum drying, PS@PDA-BN-LDH material with layered bimetallic hydroxide (LDH) is obtained.

[0107] (4) The PS@PDA-BN-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 350°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 550°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is a hollow carbon microsphere-supported boron nitride and layered bimetallic oxide material, denoted as HC@BN-LDO.

[0108] (5) Disperse the product obtained in step (4) in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 3 g / L. Place a clean polyester fabric in the buffer solution and react at 50°C and a shaking speed of 250 r / min. After 24 h, dry the fabric in an oven to obtain the fabric with cooling and antibacterial functions.

[0109] Comparative Example 1

[0110] A method for preparing a modified fabric includes the following steps:

[0111] (1) Dissolve 75µM PVP and 38mM AIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. The synthesized PS particles are filtered and washed to remove residual styrene and PVP. The obtained sample is dried in a vacuum oven to obtain PS microspheres.

[0112] (2) Disperse 1 g / L of the PS microspheres obtained in step (1) in 2 g / L Tris buffer containing 0.2 g / L dopamine, shake and dry in an oven to obtain PS@PDA precursor coated with polydopamine on the surface of PS;

[0113] (3) Dissolve 0.25g CuSO4, 0.7g ZnSO4, and 0.4g Al2(SO4)3 in 50mL of deionized water, add 2g / LPS@PDA precursor to the metal salt solution for dispersion, then add 5mL of 20% ammonia water to the mixture, dissolve it completely, then transfer it to a hydrothermal reactor and react at 100℃ for 6h, and vacuum dry to obtain PS@PDA-LDH material supported on layered bimetallic hydroxide (LDH);

[0114] (4) The PS@PDA-LDH obtained in step (3) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 350°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 550°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected, which is the carbon microsphere-supported layered bimetallic oxide material HC@LDO with a hollow structure.

[0115] (5) The product obtained in step (4) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 1 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 100 r / min. After 6 h, the fabric is dried in an oven to obtain the modified fabric.

[0116] Comparative Example 2

[0117] A method for preparing a modified fabric includes the following steps:

[0118] (1) Dissolve 75µM PVP and 38mM MAIBA in 500mL of deionized water in a three-necked flask, add 0.96mM styrene, gradually raise the reaction temperature to 70℃ and keep it at that temperature for 24h, and finally cool the mixture to room temperature. Filter and wash the synthesized PS particles to remove residual styrene and PVP, and dry the obtained sample in a vacuum oven to obtain PS microspheres.

[0119] (2) Disperse 1 g / L of the PS microspheres obtained in step (1) in 2 g / L Tris buffer containing 0.2 g / L dopamine and 7 g / L boron nitride nanosheets, shake and dry in an oven to obtain the precursor PS@PDA-BN coated with polydopamine and BN nanosheets on the surface of PS.

[0120] (3) The PS@PDA-BN obtained in step (2) is placed in a tube furnace and calcined under argon protection. The temperature is increased to 350°C at a rate of 5°C / min and held for 4 hours. Then, the temperature is increased to 550°C at a rate of 2°C / min and held for 3 hours to obtain the final product. Finally, the calcined product is collected to obtain the carbon microsphere-supported boron nitride material HC@BN with a hollow structure.

[0121] (4) The product obtained in step (3) is dispersed in a buffer solution containing 3 g / L aqueous acrylic acid to form a stable suspension with a concentration of 1 g / L. A clean polyester fabric is placed in the buffer solution and reacted at 20°C and a shaking speed of 100 r / min. After 6 h, the fabric is dried in an oven to obtain the modified fabric.

[0122] The modified fabrics of the above embodiments and comparative examples were subjected to performance tests, the details of which are as follows.

[0123] 1. Cooling performance: The cooling performance of the fabric is tested according to GB / T 35263-2017 "Test and evaluation of the instantaneous cooling performance of textiles upon contact".

[0124] 2. Antibacterial properties: In accordance with GB / T20944.3-2008 standard, the antibacterial rate of Escherichia coli in the modified fabric was tested before washing and after 30 washes.

[0125] Table 1 Performance test results of the fabrics obtained in the embodiments of the present invention

[0126]

[0127] As shown in the table, the antibacterial and thermal conductivity properties of the fabric increase simultaneously with the increase in the concentration of the mixture. Furthermore, the robust loading of boron nitride and layered bimetallic hydroxides requires the abundant functional groups on the dopamine surface, and increasing the concentration of the dopamine buffer also enhances their performance; excellent performance was also demonstrated when processing different fabrics.

[0128] The difference between Comparative Example 1 and Example 1 is the absence of boron nitride. Analysis of the data clearly shows a significant decrease in the instantaneous cooling value compared to Example 1, demonstrating that boron nitride effectively enhances the cooling sensation of the fabric in this invention. The difference between Comparative Example 2 and Example 1 is the absence of layered bimetallic compounds. Analysis of the data clearly shows a significant decrease in the antibacterial rate against E. coli in Comparative Example 1 compared to Example 1, demonstrating that layered bimetallic compounds effectively enhance the antibacterial ability of the fabric in this invention.

[0129] Comprehensive analysis of the data revealed that the optimal performance of the fabric can only be obtained by adjusting the concentration of each component in the mixture and the concentration of the dopamine buffer.

[0130] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A fabric with cooling and antibacterial functions, characterized in that, It is formed by finishing a fabric, wherein the working solution used in the finishing process contains an adhesive and a functional finishing agent, wherein the functional finishing agent is an antibacterial multifunctional material; The preparation method of the antibacterial multifunctional material includes the following steps: S1. Polystyrene microspheres are dispersed in a buffer solution containing dopamine and boron nitride nanosheets to obtain a dispersion. The dispersion is then subjected to shaking treatment to coat the surface of the polystyrene microspheres with polydopamine and boron nitride nanosheets to form a precursor. S2. The precursor is mixed with a metal salt and subjected to hydrothermal treatment under alkaline conditions. After drying, a composite material loaded with layered bimetallic hydroxides is obtained. The metal salt includes a soluble divalent metal salt and a soluble trivalent metal salt. The divalent metal ion in the soluble divalent metal salt is Cu. 2+ Ni 2+ Zn 2+ Fe 2+ Mg 2+ One or two of the following; the trivalent metal ion in the soluble trivalent metal salt is Ti. 3+ Fe 3+ Al 3+ Ni 3+ Cr 3+ One or two of them; S3. Under a protective atmosphere, the composite material is calcined to decompose the organic matter and form a hollow structure, thereby obtaining an antibacterial multifunctional material.

2. The fabric with cooling and antibacterial functions according to claim 1, characterized in that, In step S1 of the method for preparing the antibacterial multifunctional material, the polystyrene microspheres are prepared by the following operation: polyvinylpyrrolidone, 2,2′-azobisisobutylamidine dihydrochloride and styrene monomer are mixed in water, then heated to react, and the polystyrene microspheres are obtained by separation. The concentration of the polyvinylpyrrolidone is 75~600µM, and the concentration of the azobisisobutylamidine dihydrochloride is 1.2~38mM.

3. The fabric with cooling and antibacterial functions according to claim 1, characterized in that, In step S1 of the preparation method of the antibacterial multifunctional material, the concentration of polystyrene microspheres in the dispersion is 1~3 g / L, the concentration of dopamine is 0.2~5 g / L, and the concentration of boron nitride nanosheets is 7~10 g / L. The buffer solution is a Tris buffer solution or a carbonate buffer solution.

4. The fabric with cooling and antibacterial functions according to claim 1, characterized in that, In step S2 of the preparation method of the antibacterial multifunctional material, the anions in the soluble divalent metal salt and the soluble trivalent metal salt are Cl- and Cl-, respectively. - NO3 - CO3 2- SO4 2- One of them.

5. The fabric with cooling and antibacterial functions according to claim 1, characterized in that, In step S2 of the preparation method of the antibacterial multifunctional material, the alkaline condition is achieved by using sodium hydroxide and / or ammonia; the amount of precursor added is 1~5 g / L; and the temperature of the hydrothermal treatment is 95~110℃.

6. The fabric with cooling and antibacterial functions according to any one of claims 1-5, characterized in that, In step S3 of the preparation method of the antibacterial multifunctional material, calcining the composite material includes: heating to 350~450℃ at a rate of 1-5℃ / min and holding for 3-5 hours; then heating to 550~650℃ at a rate of 1-3℃ / min and holding for 2-4 hours, thus obtaining the final product.

7. The fabric with cooling and antibacterial functions according to claim 1, characterized in that, The adhesive is water-based acrylic; the fabric is polyester and / or cotton fiber fabric.

8. The method for preparing the fabric with cooling and antibacterial functions as described in claim 1, characterized in that, include: The functional finishing agent is dispersed in a solution containing a binder to obtain a suspension; The fabric is placed in the suspension, subjected to agitation, and then dried to obtain the fabric with cooling and antibacterial functions.

9. The method for preparing a fabric with cooling and antibacterial functions according to claim 8, characterized in that, The concentrations of the functional finishing agent and the adhesive in the suspension are 1~3g / L, respectively; the fabric is a clean fabric that has been soaked and washed with water and ethanol in sequence and then dried; the temperature of the oscillation treatment is 20~50℃ and the oscillation speed is 100-300r / min.

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