A fast-response heat-stable antibacterial and antiviral agent and its preparation method and application

Abstract

The present invention belongs to the technical field of preparation of antibacterial and antiviral agents, and relates to a fast-response thermally stable antibacterial and antiviral agent and its preparation method and application. Preparation method: adding a mixture of TiO2 nanopowder, alkali, Cu 2+ 、Ag + A reducing agent solution is added dropwise to the dispersion, and after the addition is completed, the mixture is stirred and reacted at 20-50°C for 2-5 hours. After post-treatment, a fast-response heat-stable antibacterial and antiviral agent is obtained. The obtained fast-response heat-stable antibacterial and antiviral agent is a micron-sized sphere formed by self-assembly of composite particles. Application: The fast-response heat-stable antibacterial and antiviral agent is melt-blended with polymer powder to form an antibacterial masterbatch, and the antibacterial masterbatch and polymer chips are melt-spun to form antibacterial and antiviral fibers. The fast-response heat-stable antibacterial and antiviral agent of the present invention can meet the requirements of fast-response sterilization while having good thermal stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of antibacterial and antiviral agents, and relates to a fast-response thermally stable antibacterial and antiviral agent, a preparation method thereof, and an application thereof. Background Art

[0002] Microorganisms such as bacteria and viruses are widely distributed in nature and are important pathogens that cause biological diseases. Their transmission between people contributes to the spread of infectious diseases. Contact transmission is a major route of transmission for pathogenic microorganisms, particularly among susceptible individuals who come into contact with everyday items contaminated by infectious sources. Textiles, as common household items, offer a suitable environment for microorganisms to attach and grow, thanks to their unique woven structure, numerous gaps, and excellent thermal and moisture-retaining properties.

[0003] Textiles that rapidly kill microorganisms offer significant advantages in inhibiting the spread of disease. Efficiently killing bacteria and viruses in textiles within a short period of time can significantly reduce the risk of re-transmission, which is particularly important for healthcare workers and vulnerable populations. However, research and development of fast-acting antibacterial and antiviral agents for melt spinning applications is relatively limited.

[0004] Existing high-temperature-resistant inorganic antimicrobial agents, such as the one disclosed in patent application CN117886608A, have a strong inhibitory effect against Escherichia coli, exceeding 99%. However, SEM images show that the powder is nanoparticles with no special surface structure, which may cause agglomeration. The antimicrobial agent disclosed in patent application CN114847279A boasts an antimicrobial rate of over 99.9% against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. However, the use of cullet as a raw material can be irritating to the human body, and the powder's particle size exceeding 10 μm limits its application. Furthermore, the aforementioned patents do not specify the response time of their antimicrobial effects, making it difficult to determine whether they can meet the requirements for inhibiting the transmission of microorganisms from objects to humans.

[0005] Among organic antimicrobial agents, the quaternary ammonium salt antimicrobial used in the literature (J.Appl.Polym.Sci.2015,132,42702.) coated the surface of cellulose fibers and effectively inactivated Escherichia coli and Staphylococcus aureus within 10 minutes. However, the thermal stability of the organic antimicrobial agent cannot be guaranteed. The cellulose membrane material obtained by the treatment method in the literature (Macromol.Mater.Eng.2020,305,2000228.) achieved an inhibition rate of 99.45% against Staphylococcus aureus and 73.47% against Escherichia coli within 5 minutes. However, according to the literature, thermal decomposition of the material occurs at 232°C, and heat loss is around 50% below 350°C. The heat resistance is poor and cannot meet the temperature requirement of melt spinning above 300°C.

[0006] In summary, the antibacterial and antiviral agents in the prior art cannot simultaneously meet the requirements of rapid response sterilization and good thermal stability. Summary of the Invention

[0007] The purpose of the present invention is to solve the problems existing in the prior art and provide a fast-response heat-stable antibacterial and antiviral agent and a preparation method and application thereof.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A fast-response, heat-stable antibacterial and antiviral agent, comprising micron-sized spheres self-assembled from composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres; the mixed-phase TiO2 nanopowder is a mixture of anatase-type TiO2 nanopowder and rutile-type TiO2 nanopowder; the Cu2O crystals are in-situ grown on the surface of the mixed-phase TiO2 nanopowder; and the Ag nanospheres are embedded in and on the surface of the Cu2O crystals.

[0010] As the preferred technical solution:

[0011] The fast-response thermally stable antibacterial and antiviral agent described above, wherein the average particle sizes of the mixed-phase TiO2 nanopowder, Cu2O crystals, Ag nanospheres, composite particles, and the fast-response thermally stable antibacterial and antiviral agent are 20-50 nm, 10-50 nm, 5-15 nm, 40-300 nm, and 0.6-1.5 μm, respectively;

[0012] In the fast-response thermally stable antibacterial and antiviral agent, the content of the mixed-phase TiO2 nano-powder is 20-40 wt%, and the content of the Cu2O crystal is 40-60 wt%.

[0013] The fast-response heat-stable antibacterial and antiviral agent described above has an antibacterial rate of more than 95% against Escherichia coli and Staphylococcus aureus within 5 minutes, an antiviral rate of more than 92% against HCoV-OC43 and HCoV-229E viruses within 5 minutes, an antibacterial rate of more than 99% against Escherichia coli and Staphylococcus aureus within 30 minutes, and an antiviral rate of more than 99% against HCoV-OC43 and HCoV-229E viruses within 30 minutes, and a thermal weight loss within 330°C of less than 5wt%.

[0014] The present invention also provides a method for preparing a fast-response thermally stable antibacterial and antiviral agent as described above, wherein a template-free method is used to prepare a mixture of TiO2 nanopowder, alkali, Cu 2+ 、Ag + The reducing agent solution is added dropwise to the dispersion, and after the addition is completed, the mixture is stirred and reacted at 20-50° C. for 2-5 hours. After post-treatment (separation, washing, and drying at 50-80° C.), a fast-response thermally stable antibacterial and antiviral agent is obtained.

[0015] The present invention adopts reducing agent to 2+ Reduced to Cu2O crystals, mixed phase TiO2 nano-scale powders were introduced into the reaction solution as heterogeneous nucleation nuclei, inducing Cu2O crystals to grow on the mixed phase TiO2 nano-scale powders. The Cu2O crystals and the mixed phase TiO2 nano-scale powders had a large contact area. 2+ During the reduction process, Ag + It is also synchronously reduced to Ag nanospheres, which are embedded in the interior and surface of the Cu2O crystals to obtain composite particles. The composite particles have a high surface energy in the reaction solution and tend to self-assemble to reduce the surface energy, and agglomerate with each other. During the agglomeration process, certain pores are opened between the particles, and finally a stable, fast-responding, heat-stable antibacterial and antiviral agent is obtained.

[0016] Numerous literature, including (Small, 2023, 19(26), 2300394.) and (Chemical Reviews, 2016, 116(18): 10983-11060.), summarizes and records the synthesis methods of micro-nanostructured particles. Among these methods, the template method is currently the most widely recognized one. This method uses existing template agents such as polymers carrying functional groups that can react with metal ions to restrict the directional growth of particle crystals, thereby forming micro-nanostructured particles that meet the requirements. However, the introduction of templates may bring some problems. On the one hand, it may affect the thermal stability of the particles, making the antibacterial and antiviral agents unable to meet the temperature requirements of melt spinning above 300°C; on the other hand, the template may dilute the effective antibacterial components in the antibacterial and antiviral agents, thereby damaging their antibacterial effect at the same addition amount and increasing the synthesis cost of the antibacterial and antiviral agents.

[0017] Although the literature (Exploration, 2022, 2(5), 20210237.) and other literature have introduced methods for synthesizing micro-nanostructures without templates, these methods have some limitations in practical applications. On the one hand, the synthesis conditions of such methods are relatively harsh, and often require a specific temperature or solvent environment to achieve effective synthesis of micro-nanostructures; on the other hand, these methods are more often used to synthesize single-phase micro-nanostructure particles, that is, they are mainly suitable for the synthesis of particles with a single chemical composition. However, when attempting to synthesize two-phase or even multi-phase particles such as TiO2 and Cu2O, these methods often face more limitations and challenges. Therefore, although the template-free synthesis of micro-nanostructures has certain potential, there are still certain limitations in achieving the synthesis of complex particle structures.

[0018] In contrast, the present invention conducts the reaction in an aqueous environment at room temperature, which is mild and environmentally friendly. Notably, the present invention does not use high-molecular-weight organic templates, which results in a product with improved thermal stability. In this way, the present invention achieves efficient and low-cost synthesis of antibacterial and antiviral agents suitable for melt spinning.

[0019] As the preferred technical solution:

[0020] The method as described above comprises the following steps:

[0021] (1) Slowly add copper salt solution and silver salt solution to the alkaline solution in sequence, and stir and mix for 1 to 3 hours;

[0022] (2) After adding the mixed phase TiO2 nanopowder, stirring until the mixed phase TiO2 nanopowder is fully dispersed;

[0023] (3) Slowly add the reducing agent solution dropwise, and after the addition is completed, stir and react at 20-50° C. for 2-5 hours. After post-treatment, a fast-response thermally stable antibacterial and antiviral agent is obtained.

[0024] In the above method, the concentrations of the alkali solution, copper salt solution, silver salt solution, and reducing agent solution are 0.1-0.5 M, 0.3-1.5 M, 0.01-0.1 M, and 0.5-2.0 M, respectively;

[0025] The base is NaOH, KOH or ammonia water, the copper salt is copper acetate, copper nitrate or copper sulfate, the silver salt is silver nitrate, and the reducing agent is ascorbic acid, sodium sulfite or hydrazine hydrate;

[0026] The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:0.5-1.5:1.5-2, and the molar ratio of the mixed phase TiO2 nanometer powder and the copper salt is 1:2-5.

[0027] According to the method described above, the stirring reaction is carried out at 0.1 MPa and the stirring rate is 200-500 rpm.

[0028] The present invention also provides a use of a fast-response heat-stable antibacterial and antiviral agent as described above, which is used as an additive for melt spinning.

[0029] As the preferred technical solution:

[0030] For the application described above, the specific process is: first, the fast-response heat-stable antibacterial and antiviral agent is melt-blended with the polymer powder to make an antibacterial masterbatch, and then the antibacterial masterbatch and the polymer chips are melt-spun to make antibacterial and antiviral fibers.

[0031] In the application described above, the polymer powder and the polymer chips are made of the same material, PET or PA6; the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; and the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial and antiviral fiber is 1.6-5wt%.

[0032] Principle of the invention:

[0033] The fast-response heat-stable antibacterial and antiviral agent of the present invention can meet the requirements of fast-response sterilization for the following reasons:

[0034] (1) TiO2 is the first N-type semiconductor to be studied, but TiO2 semiconductor has a wide excitation band gap problem and can only be excited by ultraviolet light with higher energy, and has poor utilization of visible light. Cu2O is a rare P-type semiconductor that can be excited under visible light. Precious metal nanoparticles such as Ag have the SPR effect. Its presence can expand the scope of semiconductor materials to utilize sunlight, extend light absorption from ultraviolet light to visible light and infrared light segments, and enhance the photocatalytic effect. The three can be combined to form a PN junction structure with a high response rate to sunlight at the contact interface between TiO2 and Cu2O, and the excitation band gap of the PN junction can be reduced by Ag, so that the material can have a better photocatalytic effect under irradiation of light with lower energy. Specifically, this PN junction will produce directional carrier migration under sunlight irradiation, and the negative charge of the N region will be transferred to the P region (Cu2O region) and induce the production of free radicals that are destructive to pathogenic microorganisms in the P region, thereby enhancing the original antibacterial properties of inorganic antibacterial and antiviral agents.

[0035] (2) The present invention adopts mixed-phase TiO2 nanopowder as the nucleus for heterogeneous nucleation of Cu2O. Compared with pure anatase TiO2 nanopowder or rutile TiO2 nanopowder, the mixed-phase TiO2 nanopowder increases the defect density in the TiO2 lattice due to the mixing of the two structures, increases the concentration of carriers, and increases the number of electrons and holes, so that it has a stronger ability to capture solution components on the TiO2 surface, and has excellent ultraviolet absorption, photocatalytic sterilization, decomposition of organic pollutants and other properties. Moreover, due to the nanostructure of the particles themselves, the specific surface area is larger, and the irregular mixed-phase structure makes the growth sites on the surface easy for crystal attachment unevenly distributed. This causes Cu2O crystals to select suitable sites on the TiO2 surface and grow relatively randomly, making it difficult to completely cover the original TiO2. Both TiO2 and Cu2O are exposed to participate in the photocatalytic process, and the original antibacterial and photothermal conversion capabilities of TiO2 are fully utilized. For example, the photothermal conversion of TiO2 is achieved by absorbing infrared light and converting it into heat energy. However, infrared light has low energy and poor penetration. Actively exposing TiO2 from Cu2O can also enhance the effect of TiO2 photothermal conversion. In addition, Cu2O crystals grow in situ on the surface of the mixed-phase TiO2 nanopowder, and the two have a relatively large contact area, which is difficult to achieve through simple physical blending or simultaneous growth of two phases. The larger the contact area, the easier it is for PN junction charge transfer to occur, the more active free radicals are generated by catalysis, and the better the photocatalytic antibacterial effect.

[0036] (3) The micron-sized spheres of the present invention are formed by self-assembly of composite particles. The composite particles are arranged non-densely during the self-assembly process, and there is a certain space between them, so that a large number of large-pore-sized gaps are formed on the surface of the antibacterial and antiviral agent (which can be observed based on scanning electron microscope images), which can embed and fix viruses, providing more sufficient space for virus enrichment.

[0037] (4) The composite photothermal antibacterial and antiviral agent of the present invention has a surface concave-convex structure, which helps to further adhere to the virus and exert a more effective antiviral effect.

[0038] (5) Ag, Ti, and Cu all have certain antibacterial effects. When used in combination, they can enhance the broad-spectrum antibacterial properties of antibacterial and antiviral agents. Existing literature has shown that Ag nanoparticles (Molecules, 2011, 16(10):8894-8918) and Cu2O (ChemPlusChem, 2020, 85(9):1949-2206) also have inhibitory effects on viruses.

[0039] (6) TiO2 has a photothermal conversion effect, which can absorb infrared light and convert it into heat, causing the temperature to rise and inhibiting the growth and reproduction of bacteria.

[0040] At the same time, the fast-response thermally stable antibacterial and antiviral agent of the present invention can meet the requirements of melt spinning because: ① The present invention does not use a large molecular weight organic template in the process of preparing the fast-response thermally stable antibacterial and antiviral agent, which makes the product have better thermal stability; ② The particle size of the composite photothermal antibacterial and antiviral agent is uniform and controllable; ③ The composite photothermal antibacterial and antiviral agent has relatively good compatibility with the polymer matrix and will not have a significant impact on the mechanical properties of the fiber.

[0041] Beneficial effects:

[0042] The present invention superimposes the original antibacterial and antiviral effects of antibacterial and antiviral agents, the generation of active free radicals by PN junction photocatalysis, and the antibacterial effect of TiO2 photothermal effect, and constructs a micro-nano structure in morphology to construct a composite antibacterial and antiviral agent that can respond quickly. It can not only quickly respond and kill bacteria, but also has a good inhibitory effect on viruses, and at the same time has good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a SEM image of the fast-response thermally stable antibacterial and antiviral agent prepared in Example 3;

[0044] Figure 2 This is a SEM image of the fast-response thermally stable antibacterial and antiviral agent prepared in Example 4;

[0045] Figure 3This is a SEM image of the fast-response thermally stable antibacterial and antiviral agent prepared in Example 2;

[0046] Figure 4 This is a SEM image of the fast-response thermally stable antibacterial and antiviral agent prepared in Example 5;

[0047] Figure 5 This is an SEM image of the fast-response thermally stable antibacterial and antiviral agent prepared in Example 1. DETAILED DESCRIPTION

[0048] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0049] The test methods for the relevant performance indicators in the following embodiments are as follows:

[0050] Antibacterial rate: tested in accordance with GB / T 21510-2008 standard.

[0051] Antiviral rate: Tested in accordance with ISO 18184-2019 standard.

[0052] Thermal weight loss of fast-response heat-stable antibacterial and antiviral agents within 330°C: The test was conducted using a TG209F1 Netzsch thermogravimetric analyzer in a nitrogen atmosphere; the purge gas rate was 40 mL / min, the protective gas rate was 20 mL / min, the heating rate was 10°C / min, and the actual test range was 30-700°C.

[0053] Example 1

[0054] A method for preparing a fast-response heat-stable antibacterial and antiviral agent, comprising the following steps:

[0055] (1) Preparation of raw materials;

[0056] Alkaline solution: the solute is NaOH, the solvent is water, and the concentration is 0.2M;

[0057] Copper salt solution: the solute is copper acetate, the solvent is water, and the concentration is 0.3M;

[0058] Silver salt solution: the solute is silver nitrate, the solvent is water, and the concentration is 0.01M;

[0059] Mixed-phase TiO2 nanopowder: fumed titanium dioxide, manufactured by Evonik Degussa, Germany, model AEROXIDE P25;

[0060] Reducing agent solution: the solute is ascorbic acid, the solvent is water, and the concentration is 0.5M;

[0061] (2) Preparation of a fast-response thermally stable antibacterial and antiviral agent, the specific steps are as follows:

[0062] (2.1) Slowly add copper salt solution and silver salt solution to the alkaline solution dropwise, stirring for 3 hours;

[0063] (2.2) After adding the mixed phase TiO2 nanopowder to the system, stirring until the mixed phase TiO2 nanopowder is fully dispersed;

[0064] (2.3) Slowly dropwise adding the reducing agent solution to the system, stirring the mixture at 200 rpm and 0.1 MPa at 20°C for 3 h, and then post-processing (separation, washing, and drying at 60°C) to obtain a fast-response thermally stable antibacterial and antiviral agent;

[0065] The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:0.5:1.5, and the molar ratio of the mixed phase TiO2 nanopowder and the copper salt is 1:2.

[0066] The scanning electron microscope image of the finally prepared fast-response thermally stable antibacterial and antiviral agent is as follows: Figure 5 As shown, the fast-response thermally stable antibacterial and antiviral agent is a micron-sized sphere formed by self-assembly of composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres. The Cu2O crystals are in situ grown on the surface of the mixed-phase TiO2 nanopowder, and the Ag nanospheres are embedded in the interior and surface of the Cu2O crystals.

[0067] The average particle size of the mixed-phase TiO2 nanopowder is 20 nm, the average particle size of the Cu2O crystals is 10 nm, the average particle size of the Ag nanospheres is 5 nm, the average particle size of the composite particles is 40 nm, and the average particle size of the fast-response thermally stable antibacterial and antiviral agent is 1.2 μm. The content of the mixed-phase TiO2 nanopowder in the fast-response thermally stable antibacterial and antiviral agent is 20 wt%, and the content of the Cu2O crystals is 40 wt%.

[0068] The rapid-response heat-stable antibacterial and antiviral agent had an antibacterial rate of 99.8% against Escherichia coli and 99.6% against Staphylococcus aureus within 5 minutes. The rapid-response heat-stable antibacterial and antiviral agent had an antiviral rate of 96.6% against HCoV-OC43 and 94.4% against HCoV-229E within 5 minutes.

[0069] The fast-response heat-stable antibacterial and antiviral agent has an antibacterial rate of 99.9% against Escherichia coli and 99.9% against Staphylococcus aureus within 30 minutes; the fast-response heat-stable antibacterial and antiviral agent has an antiviral rate of 99.9% against HCoV-OC43 virus and 99.9% against HCoV-229E virus within 30 minutes; the thermal weight loss of the fast-response heat-stable antibacterial and antiviral agent within 330°C is 4.22wt%.

[0070] An application of a fast-response heat-stable antibacterial and antiviral agent, first melt-blending the fast-response heat-stable antibacterial and antiviral agent prepared in this embodiment with PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FG600) powder to prepare an antibacterial masterbatch, then melt-spinning the antibacterial masterbatch and PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FD501) slices to prepare an antibacterial and antiviral fiber; wherein the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; melt-blending The process parameters are: screw zone 1 temperature 230℃, zone 2 temperature 245℃, zone 3 temperature 260℃, zone 4 temperature 255℃, zone 5 temperature 255℃, zone 6 temperature 255℃, zone 7 temperature 255℃; head temperature control 260℃; melt spinning process parameters are: screw zone 1 temperature 285℃, zone 2 temperature 297℃, zone 3 temperature 290℃, zone 4 temperature 292℃; one roller winding speed 900m / min, one roller temperature 60℃; two roller winding speed 1800m / min, two roller temperature 60℃.

[0071] The content of the fast-response heat-stable antibacterial and antiviral agent in the finally prepared antibacterial and antiviral fiber is 3.2 wt %.

[0072] Example 2

[0073] A method for preparing a fast-response heat-stable antibacterial and antiviral agent, comprising the following steps:

[0074] (1) Preparation of raw materials;

[0075] Alkaline solution: the solute is NaOH, the solvent is water, and the concentration is 0.2M;

[0076] Copper salt solution: the solute is copper sulfate, the solvent is water, and the concentration is 0.3M;

[0077] Silver salt solution: the solute is silver nitrate, the solvent is water, and the concentration is 0.01M;

[0078] Mixed-phase TiO2 nanopowder: fumed titanium dioxide, manufactured by Evonik Degussa, Germany, model AEROXIDE P25;

[0079] Reducing agent solution: the solute is ascorbic acid, the solvent is water, and the concentration is 0.5M;

[0080] (2) Preparation of a fast-response thermally stable antibacterial and antiviral agent, the specific steps are as follows:

[0081] (2.1) Slowly add copper salt solution and silver salt solution to the alkaline solution dropwise, stirring for 3 hours;

[0082] (2.2) After adding the mixed phase TiO2 nanopowder to the system, stirring until the mixed phase TiO2 nanopowder is fully dispersed;

[0083] (2.3) Slowly add the reducing agent solution dropwise to the system. After the addition is complete, stir the mixture at 200 rpm and 0.1 MPa at 40°C for 3 h. After post-treatment (separation, washing, and drying at 60°C), a fast-response thermally stable antibacterial and antiviral agent is obtained.

[0084] The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:0.5:1.5, and the molar ratio of the mixed phase TiO2 nanopowder and the copper salt is 1:2.

[0085] The scanning electron microscope image of the finally prepared fast-response thermally stable antibacterial and antiviral agent is as follows: Figure 3 As shown, the fast-response thermally stable antibacterial and antiviral agent is a micron-sized sphere formed by self-assembly of composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres. The Cu2O crystals are in situ grown on the surface of the mixed-phase TiO2 nanopowder, and the Ag nanospheres are embedded in the interior and surface of the Cu2O crystals.

[0086] The average particle size of the mixed-phase TiO2 nanopowder is 20 nm, the average particle size of the Cu2O crystals is 50 nm, the average particle size of the Ag nanospheres is 5 nm, the average particle size of the composite particles is 240 nm, and the average particle size of the fast-response thermally stable antibacterial and antiviral agent is 0.6 μm. The content of the mixed-phase TiO2 nanopowder in the fast-response thermally stable antibacterial and antiviral agent is 30 wt%, and the content of the Cu2O crystals is 50 wt%.

[0087] The rapid-response heat-stable antibacterial and antiviral agent had an antibacterial rate of 99.8% against Escherichia coli and 97.6% against Staphylococcus aureus within 5 minutes. The rapid-response heat-stable antibacterial and antiviral agent had an antiviral rate of 92.1% against HCoV-OC43 and 92% against HCoV-229E within 5 minutes.

[0088] The fast-response heat-stable antibacterial and antiviral agent has an antibacterial rate of 99.9% against Escherichia coli and 99.9% against Staphylococcus aureus within 30 minutes; the fast-response heat-stable antibacterial and antiviral agent has an antiviral rate of 99.8% against HCoV-OC43 virus and 99.7% against HCoV-229E virus within 30 minutes; the thermal weight loss of the fast-response heat-stable antibacterial and antiviral agent within 330°C is 1.44wt%.

[0089] An application of a fast-response heat-stable antibacterial and antiviral agent, first melt-blending the fast-response heat-stable antibacterial and antiviral agent prepared in this embodiment with PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FG600) powder to prepare an antibacterial masterbatch, then melt-spinning the antibacterial masterbatch and PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FD501) slices to prepare an antibacterial and antiviral fiber; wherein the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; melt-blending The process parameters are: screw zone 1 temperature 230℃, zone 2 temperature 245℃, zone 3 temperature 260℃, zone 4 temperature 255℃, zone 5 temperature 255℃, zone 6 temperature 255℃, zone 7 temperature 255℃; head temperature control 260℃; melt spinning process parameters are: screw zone 1 temperature 285℃, zone 2 temperature 297℃, zone 3 temperature 290℃, zone 4 temperature 292℃; one roller winding speed 900m / min, one roller temperature 60℃; two roller winding speed 1800m / min, two roller temperature 60℃.

[0090] The content of the fast-response heat-stable antibacterial and antiviral agent in the finally prepared antibacterial and antiviral fiber is 3.2 wt %.

[0091] Example 3

[0092] A method for preparing a fast-response heat-stable antibacterial and antiviral agent, comprising the following steps:

[0093] (1) Preparation of raw materials;

[0094] Alkaline solution: the solute is NaOH, the solvent is water, and the concentration is 0.3M;

[0095] Copper salt solution: the solute is copper nitrate, the solvent is water, and the concentration is 1.5M;

[0096] Silver salt solution: the solute is silver nitrate, the solvent is water, and the concentration is 0.05M;

[0097] Mixed-phase TiO2 nanopowder: nano titanium dioxide, manufactured by Hangzhou Hengna New Materials Co., Ltd., model HN-J25;

[0098] Reducing agent solution: the solute is sodium sulfite, the solvent is water, and the concentration is 2.0M;

[0099] (2) Preparation of a fast-response thermally stable antibacterial and antiviral agent, the specific steps are as follows:

[0100] (2.1) Slowly add copper salt solution and silver salt solution to the alkaline solution, stirring for 1 hour.

[0101] (2.2) After adding the mixed phase TiO2 nanopowder to the system, stirring until the mixed phase TiO2 nanopowder is fully dispersed;

[0102] (2.3) Slowly dropwise adding the reducing agent solution to the system, stirring the mixture at 350 rpm under 0.1 MPa and 20°C for 5 h, and then post-processing (separation, washing, and drying at 80°C) to obtain a fast-response thermally stable antibacterial and antiviral agent.

[0103] The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:1.5:2, and the molar ratio of the mixed phase TiO2 nanopowder and the copper salt is 1:5.

[0104] The scanning electron microscope image of the finally prepared fast-response thermally stable antibacterial and antiviral agent is as follows: Figure 1 As shown, micron-scale spheres are formed by self-assembly of composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres. The Cu2O crystals are in situ grown on the surface of the mixed-phase TiO2 nanopowder, and the Ag nanospheres are embedded in the interior and surface of the Cu2O crystals.

[0105] The average particle size of the mixed-phase TiO2 nanopowder is 25 nm, the average particle size of the Cu2O crystals is 20 nm, the average particle size of the Ag nanospheres is 7 nm, the average particle size of the composite particles is 160 nm, and the average particle size of the fast-response thermally stable antibacterial and antiviral agent is 0.9 μm. The content of the mixed-phase TiO2 nanopowder in the fast-response thermally stable antibacterial and antiviral agent is 40 wt%, and the content of the Cu2O crystals is 40 wt%.

[0106] The rapid-response heat-stable antibacterial and antiviral agent had an antibacterial rate of 95.9% against Escherichia coli and 96.4% against Staphylococcus aureus within 5 minutes. The rapid-response heat-stable antibacterial and antiviral agent had an antiviral rate of 93.2% against HCoV-OC43 and 95.4% against HCoV-229E within 5 minutes.

[0107] The fast-response heat-stable antibacterial and antiviral agent has an antibacterial rate of 99.8% against Escherichia coli and 99.5% against Staphylococcus aureus within 30 minutes; the fast-response heat-stable antibacterial and antiviral agent has an antiviral rate of 99.6% against HCoV-OC43 virus and 99.6% against HCoV-229E virus within 30 minutes; the thermal weight loss of the fast-response heat-stable antibacterial and antiviral agent within 330°C is 3.02wt%.

[0108] An application of a fast-response heat-stable antibacterial and antiviral agent, first melt-blending the fast-response heat-stable antibacterial and antiviral agent prepared in this embodiment with PA6 (manufacturer: DuPont, brand: PA6 ST7301 NC010) powder to prepare an antibacterial masterbatch, and then melt-blending the antibacterial masterbatch with PA6 (manufacturer: DuPont, brand: PA6 7304NC010) slices are melt-spun to make antibacterial and antiviral fibers; wherein, the content of the fast-response thermally stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; the process parameters of the melt blending are: screw zone 1 temperature 210°C, zone 2 temperature 225°C, zone 3 temperature 240°C, zone 4 temperature 235°C, zone 5 temperature 235°C, zone 6 temperature 235°C, zone 7 temperature 235°C; the head temperature control is 240°C; the process parameters of the melt spinning are: screw zone 1 temperature 266°C, zone 2 temperature 282°C, zone 3 temperature 272°C, zone 4 temperature 270°C; the first roller winding speed is 1500m / min, the first roller temperature is 60°C; the second roller winding speed is 3000m / min, and the second roller temperature is 120°C.

[0109] The content of the fast-response heat-stable antibacterial and antiviral agent in the finally prepared antibacterial and antiviral fiber is 5 wt %.

[0110] Comparative Example 1

[0111] A method for preparing an antibacterial and antiviral agent is basically the same as Example 3, except that the mixed-phase TiO2 nanopowder is replaced with anatase TiO2 nanopowder of equal mass (manufacturer: Hangzhou Hengna New Materials Co., Ltd., model: HN-TA18).

[0112] The antibacterial and antiviral agent had an antibacterial rate of 77.2% against Escherichia coli and 72.0% against Staphylococcus aureus within 5 minutes. The antiviral rate of the antibacterial and antiviral agent against HCoV-OC43 virus and HCoV-229E virus within 5 minutes was 47.6% and 64.6% respectively.

[0113] The antibacterial and antiviral agent had an antibacterial rate of 95.0% against Escherichia coli and 94.2% against Staphylococcus aureus within 30 minutes; the antiviral rate of the antibacterial and antiviral agent against HCoV-OC43 virus within 30 minutes was 85.3% and the antiviral rate against HCoV-229E virus was 89.0%.

[0114] Comparative Example 2

[0115] A method for preparing an antibacterial and antiviral agent is basically the same as Example 3, except that the mixed-phase TiO2 nanopowder is replaced with an equal mass of rutile TiO2 nanopowder (manufacturer: Hangzhou Hengna New Materials Co., Ltd., model: HN-T25).

[0116] The antibacterial and antiviral agent had an antibacterial rate of 82.3% against Escherichia coli and 79.9% against Staphylococcus aureus within 5 minutes. The antiviral rate of the antibacterial and antiviral agent against HCoV-OC43 virus and HCoV-229E virus within 5 minutes was 52.1% and 59.2% respectively.

[0117] The antibacterial and antiviral agent had an antibacterial rate of 95.2% against Escherichia coli and 97.7% against Staphylococcus aureus within 30 minutes; the antiviral rate of the antibacterial and antiviral agent against HCoV-OC43 virus within 30 minutes was 87.5% and the antiviral rate against HCoV-229E virus was 85.1%.

[0118] Compared with Example 3, the antibacterial and antiviral rates of the antibacterial and antiviral agents of Comparative Examples 1 and 2 within 5 minutes were significantly reduced. This is because pure anatase TiO2 nanopowder is used in Comparative Example 1, and pure rutile TiO2 nanopowder is used in Comparative Example 2. The single crystal structure makes the defect density in the TiO2 lattice smaller, the carrier concentration is reduced, and the number of electrons and holes is reduced, thereby weakening the ability to capture solution components on the TiO2 surface, and reducing the performance of ultraviolet absorption, photocatalytic sterilization, and decomposition of organic pollutants. At the same time, since it is not The mixed phase structure has a relatively small specific surface area of ​​the particles, and the surface growth sites are distributed more regularly, which makes it easy for Cu2O crystals to completely cover the original TiO2 when growing on the TiO2 surface, resulting in TiO2 and Cu2O not being fully exposed to participate in the photocatalytic process, and thus the original antibacterial and photothermal conversion capabilities of TiO2 cannot be fully exerted; in addition, the contact area between the single crystal TiO2 nanopowder and the Cu2O crystal during in-situ growth is relatively small, the PN junction charge transfer is more difficult to occur, the active free radicals generated by catalysis are reduced, and the photocatalytic antibacterial effect is worse.

[0119] Example 4

[0120] A method for preparing a fast-response heat-stable antibacterial and antiviral agent, comprising the following steps:

[0121] (1) Preparation of raw materials;

[0122] Alkaline solution: solute is KOH, solvent is water, concentration is 0.1M;

[0123] Copper salt solution: the solute is copper sulfate, the solvent is water, and the concentration is 1.5M;

[0124] Silver salt solution: the solute is silver nitrate, the solvent is water, and the concentration is 0.1M;

[0125] Mixed-phase TiO2 nanopowder: fumed titanium dioxide, manufactured by Hubei Huifu Nanomaterials Co., Ltd., model NT-50;

[0126] Reducing agent solution: the solute is ascorbic acid, the solvent is water, and the concentration is 2.0 M;

[0127] (2) Preparation of a fast-response thermally stable antibacterial and antiviral agent, the specific steps are as follows:

[0128] (2.1) Slowly add copper salt solution and silver salt solution to the alkaline solution, stirring for 2 hours.

[0129] (2.2) After adding the mixed phase TiO2 nanopowder to the system, stirring until the mixed phase TiO2 nanopowder is fully dispersed;

[0130] (2.3) Slowly dropwise adding the reducing agent solution to the system, stirring the mixture at 500 rpm under 0.1 MPa and 20°C for 3 h, and then post-processing (separation, washing, and drying at 50°C) to obtain a fast-response thermally stable antibacterial and antiviral agent;

[0131] The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:0.5:2, and the molar ratio of the mixed phase TiO2 nanopowder and the copper salt is 1:5.

[0132] The scanning electron microscope image of the finally prepared fast-response thermally stable antibacterial and antiviral agent is as follows: Figure 2 As shown, the fast-response thermally stable antibacterial and antiviral agent is a micron-sized sphere formed by self-assembly of composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres. The Cu2O crystals are in situ grown on the surface of the mixed-phase TiO2 nanopowder, and the Ag nanospheres are embedded in the interior and surface of the Cu2O crystals.

[0133] The average particle size of the mixed-phase TiO2 nanopowder is 50 nm, the average particle size of the Cu2O crystals is 40 nm, the average particle size of the Ag nanospheres is 15 nm, the average particle size of the composite particles is 300 nm, and the average particle size of the fast-response thermally stable antibacterial and antiviral agent is 1.5 μm. The content of the mixed-phase TiO2 nanopowder in the fast-response thermally stable antibacterial and antiviral agent is 30 wt%, and the content of the Cu2O crystals is 60 wt%.

[0134] The rapid-response heat-stable antibacterial and antiviral agent had an antibacterial rate of 96.1% against Escherichia coli and 96.5% against Staphylococcus aureus within 5 minutes. The rapid-response heat-stable antibacterial and antiviral agent had an antiviral rate of 96.4% against HCoV-OC43 and 97.8% against HCoV-229E within 5 minutes.

[0135] The fast-response heat-stable antibacterial and antiviral agent has an antibacterial rate of 99.5% against Escherichia coli and 99.2% against Staphylococcus aureus within 30 minutes; the fast-response heat-stable antibacterial and antiviral agent has an antiviral rate of 99.8% against HCoV-OC43 virus and 99.2% against HCoV-229E virus within 30 minutes; the thermal weight loss of the fast-response heat-stable antibacterial and antiviral agent within 330°C is 1.65wt%.

[0136] An application of a fast-response heat-stable antibacterial and antiviral agent, first melt-blending the fast-response heat-stable antibacterial and antiviral agent prepared in this embodiment with PA6 (manufacturer: DuPont, brand: PA6 ST7301 NC010) powder to prepare an antibacterial masterbatch, and then melt-blending the antibacterial masterbatch with PA6 (manufacturer: DuPont, brand: PA6 7304NC010) slices are melt-spun to make antibacterial and antiviral fibers; wherein, the content of the fast-response thermally stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; the process parameters of the melt blending are: screw zone 1 temperature 210°C, zone 2 temperature 225°C, zone 3 temperature 240°C, zone 4 temperature 235°C, zone 5 temperature 235°C, zone 6 temperature 235°C, zone 7 temperature 235°C; the head temperature control is 240°C; the process parameters of the melt spinning are: screw zone 1 temperature 266°C, zone 2 temperature 278°C, zone 3 temperature 268°C, zone 4 temperature 266°C; the first roller winding speed is 1500m / min, the first roller temperature is 60°C; the second roller winding speed is 3000m / min, and the second roller temperature is 120°C.

[0137] The content of the fast-response heat-stable antibacterial and antiviral agent in the finally prepared antibacterial and antiviral fiber is 1.6 wt %.

[0138] Example 5

[0139] A method for preparing a fast-response heat-stable antibacterial and antiviral agent, comprising the following steps:

[0140] (1) Preparation of raw materials;

[0141] Alkaline solution: the solute is ammonia water, the solvent is water, and the concentration is 0.5M;

[0142] Copper salt solution: the solute is copper acetate, the solvent is water, and the concentration is 0.3M;

[0143] Silver salt solution: the solute is silver nitrate, the solvent is water, and the concentration is 0.05M;

[0144] Mixed-phase TiO2 nanopowder: nano titanium dioxide, manufactured by Hangzhou Hengna New Materials Co., Ltd., model HN-J25;

[0145] Reducing agent solution: the solute is hydrazine hydrate, the solvent is water, and the concentration is 1.0M;

[0146] (2) Preparation of a fast-response thermally stable antibacterial and antiviral agent, the specific steps are as follows:

[0147] (2.1) Slowly add copper salt solution and silver salt solution to the alkaline solution, stirring for 1 hour.

[0148] (2.2) After adding the mixed phase TiO2 nanopowder to the system, stirring until the mixed phase TiO2 nanopowder is fully dispersed;

[0149] (2.3) Slowly dropwise adding the reducing agent solution to the system, stirring the mixture at 350 rpm under 0.1 MPa and 50°C for 2 h, and then post-processing (separation, washing, and drying at 80°C) to obtain a fast-response thermally stable antibacterial and antiviral agent.

[0150] The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:1:1.5, and the molar ratio of the mixed phase TiO2 nanopowder and the copper salt is 1:2.

[0151] The scanning electron microscope image of the finally prepared fast-response thermally stable antibacterial and antiviral agent is as follows: Figure 4 As shown, the fast-response thermally stable antibacterial and antiviral agent is a micron-sized sphere formed by self-assembly of composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres. The Cu2O crystals are in situ grown on the surface of the mixed-phase TiO2 nanopowder, and the Ag nanospheres are embedded in the interior and surface of the Cu2O crystals.

[0152] The average particle size of the mixed-phase TiO2 nanopowder is 25 nm, the average particle size of the Cu2O crystals is 10 nm, the average particle size of the Ag nanospheres is 10 nm, the average particle size of the composite particles is 120 nm, and the average particle size of the fast-response thermally stable antibacterial and antiviral agent is 0.7 μm. The content of the mixed-phase TiO2 nanopowder in the fast-response thermally stable antibacterial and antiviral agent is 40 wt%, and the content of the Cu2O crystals is 40 wt%.

[0153] The rapid-response heat-stable antibacterial and antiviral agent had an antibacterial rate of 99.5% against Escherichia coli and 96.5% against Staphylococcus aureus within 5 minutes. The rapid-response heat-stable antibacterial and antiviral agent had an antiviral rate of 93.5% against HCoV-OC43 and 92.8% against HCoV-229E within 5 minutes.

[0154] The fast-response heat-stable antibacterial and antiviral agent has an antibacterial rate of 99.7% against Escherichia coli and 99.5% against Staphylococcus aureus within 30 minutes; the fast-response heat-stable antibacterial and antiviral agent has an antiviral rate of 99.7% against HCoV-OC43 virus and 99.3% against HCoV-229E virus within 30 minutes; the thermal weight loss of the fast-response heat-stable antibacterial and antiviral agent within 330°C is 4.86wt%.

[0155] An application of a fast-response heat-stable antibacterial and antiviral agent, first melt-blending the fast-response heat-stable antibacterial and antiviral agent prepared in this embodiment with PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FG720) powder to prepare an antibacterial masterbatch, then melt-spinning the antibacterial masterbatch and PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FD502) slices to prepare an antibacterial and antiviral fiber; wherein the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; melt-blending The process parameters are: screw zone 1 temperature 230℃, zone 2 temperature 245℃, zone 3 temperature 260℃, zone 4 temperature 255℃, zone 5 temperature 255℃, zone 6 temperature 255℃, zone 7 temperature 255℃; head temperature control 260℃; melt spinning process parameters are: screw zone 1 temperature 285℃, zone 2 temperature 296℃, zone 3 temperature 290℃, zone 4 temperature 290℃; one roller winding speed 900m / min, one roller temperature 80℃; two roller winding speed 1800m / min, two roller temperature 160℃.

[0156] The content of the fast-response heat-stable antibacterial and antiviral agent in the finally prepared antibacterial and antiviral fiber is 1.6 wt %.

Claims

1. A fast-response heat-stable antibacterial and antiviral agent, characterized in that: It is a micron-sized sphere formed by self-assembly of composite particles; the composite particles are composed of mixed-phase TiO2 nanopowder, Cu2O crystals, and Ag nanospheres. The mixed-phase TiO2 nanopowder is a mixture of anatase TiO2 nanopowder and rutile TiO2 nanopowder. The Cu2O crystals are in situ grown on the surface of the mixed-phase TiO2 nanopowder, and the Ag nanospheres are embedded in the interior and surface of the Cu2O crystals.

2. A fast-response heat-stable antibacterial and antiviral agent according to claim 1, characterized in that: The average particle sizes of the mixed-phase TiO2 nanopowder, Cu2O crystal, Ag nanosphere, composite particle, and fast-response thermally stable antibacterial and antiviral agent are 20-50 nm, 10-50 nm, 5-15 nm, 40-300 nm, and 0.6-1.5 μm, respectively. In the fast-response thermally stable antibacterial and antiviral agent, the content of the mixed phase TiO2 nanopowder is 20-40wt%. The content of Cu2O crystals is 40-60 wt%.

3. A fast-response heat-stable antibacterial and antiviral agent according to claim 1, characterized in that: The fast-response heat-stable antibacterial and antiviral agent has an antibacterial rate of more than 95% against Escherichia coli and Staphylococcus aureus within 5 minutes, and an antiviral rate of more than 92% against HCoV-OC43 and HCoV-229E viruses within 5 minutes. The antibacterial rate of Escherichia coli and Staphylococcus aureus within 30 minutes reaches more than 99%, and the antiviral rate of more than 99% against HCoV-OC43 and HCoV-229E viruses within 30 minutes. The thermal weight loss within 330°C is less than 5wt%.

4. A method for preparing a fast-response heat-stable antibacterial and antiviral agent according to any one of claims 1 to 3, characterized in that: Containing mixed phase TiO2 nanometer powder, alkali, Cu 2+ 、Ag + The reducing agent solution is added dropwise to the dispersion, and after the addition is completed, the mixture is stirred and reacted at 20-50° C. for 2-5 hours. After post-treatment, a fast-response thermally stable antibacterial and antiviral agent is obtained.

5. The method according to claim 4, characterized in that The following steps are involved: (1) Add copper salt solution and silver salt solution dropwise to the alkaline solution in sequence, and stir and mix for 1 to 3 hours; (2) After adding the mixed phase TiO2 nanopowder, stirring until the mixed phase TiO2 nanopowder is fully dispersed; (3) adding a reducing agent solution dropwise, stirring and reacting at 20-50° C. for 2-5 h, and obtaining a fast-response thermally stable antibacterial and antiviral agent through post-treatment.

6. The method according to claim 5, characterized in that The concentrations of the alkali solution, copper salt solution, silver salt solution, and reducing agent solution are 0.1-0.5M, 0.3-1.5M, 0.01-0.1M, and 0.5-2.0M, respectively; The base is NaOH, KOH or ammonia water, the copper salt is copper acetate, copper nitrate or copper sulfate, the silver salt is silver nitrate, and the reducing agent is ascorbic acid, sodium sulfite or hydrazine hydrate; The volume ratio of the alkaline solution, the copper salt solution, the silver salt solution and the reducing agent solution is 1:1:0.5-1.5:1.5-2, and the molar ratio of the mixed phase TiO2 nanometer powder and the copper salt is 1:2-5.

7. The method according to claim 4, characterized in that The stirring reaction was carried out at 0.1 MPa and a stirring rate of 200 to 500 rpm.

8. Use of a fast-response heat-stable antibacterial and antiviral agent according to any one of claims 1 to 3, characterized in that: Used as an additive in melt spinning.

9. The use according to claim 8, characterized in that The specific process is: first, the fast-response heat-stable antibacterial and antiviral agent is melt-blended with polymer powder to make an antibacterial masterbatch, and then the antibacterial masterbatch and polymer chips are melt-spun to make antibacterial and antiviral fibers.

10. The use according to claim 9, characterized in that The polymer powder and the polymer chips are made of the same material, PET or PA6; the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial masterbatch is 30wt%; and the content of the fast-response heat-stable antibacterial and antiviral agent in the antibacterial and antiviral fiber is 1.6-5wt%.

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