A light response antibacterial / anti-ultraviolet polyester master batch adopting Zn / Mo-TiO2 "photon capture-physical shielding" dual mechanism synergistic effect and a preparation method thereof

Abstract

The application discloses a kind of polyester master batch of light response antibacterial / anti-ultraviolet with Zn / Mo-TiO2 "photon capture-physical shielding" dual mechanism synergistic effect and preparation method thereof, belong to functional textile technical field.The application provides a kind of Zn / Mo co-doped TiO2 Nano functional powder, realizes the widening of light response range by Zn, Mo double metal co-doping, can play excellent photocatalytic antibacterial and anti-ultraviolet performance under visible light irradiation, again cooperate the surface modification process of vacuum high temperature high-speed kneading, ensure that nano powder is evenly dispersed in polyester matrix, further improve the interfacial adhesion of powder and polyester matrix by the synergistic effect of ethylene acrylic acid copolymer and maleic anhydride graft POE, while giving polyester matrix excellent antibacterial and full-band anti-ultraviolet performance, can also ensure that the mechanical properties of composite material meet the use requirements, can be widely applied in functional textiles, medical packaging and other fields.

Description

Technical Field

[0001] This invention relates to a photoresponsive antibacterial / anti-UV polyester masterbatch with a synergistic dual mechanism of Zn / Mo-TiO2 "photon capture-physical shielding" and its preparation method, belonging to the field of functional textile technology. Background Technology

[0002] Polyester (PP) is widely used in electronics, communications, medical, construction, and packaging due to its advantages such as light weight, chemical resistance, and ease of processing, and its demand continues to increase. However, during processing, storage, and use, polymer materials are affected by external environmental factors such as light, heat, and oxygen, causing their mechanical, optical, and other physicochemical properties to gradually deteriorate. This phenomenon is called polymer aging. Polyester materials themselves do not have UV resistance. Long-term exposure to ultraviolet (UV) radiation from sunlight can easily lead to molecular chain breakage and cross-linking, resulting in brittleness, yellowing, and a significant decrease in mechanical properties, severely limiting their service life in outdoor environments. Furthermore, as a hydrophobic polymer, polyester is prone to bacterial growth on its surface, posing a potential risk in applications with high hygiene requirements, such as medical and packaging applications. Therefore, developing polyester materials that combine highly effective antibacterial properties with long-lasting UV aging resistance is of significant practical importance.

[0003] To improve the UV aging resistance of polymer materials, various solutions have been proposed in existing technologies. Among them, adding inorganic nanoparticles (such as titanium dioxide and zinc oxide) is a common method. Titanium dioxide (TiO2), as a wide-bandgap semiconductor material, can absorb photons and generate electron-hole pairs under ultraviolet irradiation, thereby effectively shielding ultraviolet rays and is widely used as an anti-UV filler. However, pure TiO2 has inherent defects such as high photogenerated carrier recombination rate, narrow ultraviolet absorption band, and weak response to visible light. When used alone, its anti-UV efficiency is limited, and it cannot impart antibacterial properties to the material.

[0004] To overcome the above shortcomings, metal ion doping modification of TiO2 has become a research hotspot. For example, Chinese patent application CN117624812A discloses a polyester acid / titanium dioxide composite film resistant to ultraviolet aging and its preparation method. This method achieves the ultraviolet aging resistance of the composite material by mixing polyester acid with iron-doped titanium dioxide, ultraviolet absorbers, and other substances. However, this technical solution has the following obvious drawbacks: First, the composition is complex, requiring the addition of organic ultraviolet absorbers in addition to metal-doped TiO2, leading to difficulties in controlling system compatibility and high production costs. Second, the single iron-doped TiO2 still faces the problem of high photogenerated carrier recombination rate, resulting in insufficient antibacterial activity and difficulty in simultaneously meeting the dual functional requirements of antibacterial and anti-ultraviolet properties.

[0005] For example, Chinese patent application CN118186627A discloses a highly efficient UV-resistant polyester industrial yarn and its preparation method. It uses a silane coupling agent to modify the surface of silver / cobalt bimetallic element-doped titanium dioxide nanoparticles and introduces the modified nanoparticles into the polyester matrix. This scheme is an improvement over single metal doping, but still has prominent technical defects: (1) Insufficient functional synergy: Although the silver / cobalt bimetallic system has certain antibacterial and UV-resistant potential, silver-based antibacterial agents are expensive and prone to oxidation and discoloration, affecting the appearance of the product; cobalt is toxic, which limits its application in sensitive fields such as medical and food packaging. (2) Poor dispersibility and interfacial compatibility: Even with the use of a silane coupling agent for surface modification, it is still difficult to achieve uniform and stable dispersion of nano-titanium dioxide particles in the polymer matrix. Due to the large specific surface area and high surface energy of nanoparticles, they are prone to secondary agglomeration during the melt blending process to prepare masterbatch, forming micron-sized agglomerates.

[0006] In existing technologies, when functional nanoparticles are melt-blended with polyester matrices to prepare functional masterbatches, the actual content of functional components in the masterbatch deviates significantly from the theoretical value due to nanoparticle agglomeration and uneven dispersion, resulting in poor batch-to-batch reproducibility. Furthermore, the presence of agglomerates significantly increases melt viscosity, increases processing torque, exacerbates equipment wear, and hinders stable industrial production.

[0007] In summary, the pressing technical problem in the existing technology lies in the lack of a modified titanium dioxide material and its functional masterbatch that can simultaneously possess highly efficient, broad-spectrum antibacterial properties and durable, wide-bandgap UV aging resistance, while exhibiting good dispersibility and interfacial compatibility in a polyester matrix, and with a stable preparation process suitable for industrial production. How to fundamentally solve the problems of nanoparticle aggregation and interfacial incompatibility in hydrophobic polymer matrices while suppressing TiO2 photogenerated carrier recombination and broadening its functional response range is a technical bottleneck that urgently needs to be overcome by those skilled in the art. Summary of the Invention

[0008] To address the aforementioned issues, this invention provides a method for preparing a Zn / Mo bimetallic synergistic TiO2 co-doping system and a unique powder surface modification technique. Through specific elemental ratios, precise process parameters, and innovative surface treatment techniques, multifunctional nanoparticles with both highly efficient photoresponsive antibacterial properties and full-band UV protection are prepared. Based on this, the multifunctional nanoparticles are combined with polyester to prepare a masterbatch for further processing.

[0009] The first objective of this invention is to provide a method for preparing photoresponsive antibacterial and UV-resistant polyester masterbatch, which is prepared from Zn / Mo co-doped TiO2 nanoparticles. The preparation method is as follows: Polyester, Zn / Mo co-doped TiO2 nanoparticles, ethylene-acrylic acid copolymer, and maleic anhydride grafts were mixed in a mass ratio of 100:5~8:0.5~2:0.5~2, melted, extruded, and pelletized to obtain a photoresponsive antibacterial and UV-resistant polyester masterbatch. The method for preparing the Zn / Mo co-doped TiO2 nanopowder includes the following steps: (1) Tetrabutyl titanate was mixed with anhydrous ethanol under a nitrogen atmosphere to obtain a titanium sol precursor solution; Zinc nitrate hexahydrate and ammonium molybdate heptahydrate are dissolved in an aqueous ethanol solution and mixed to obtain a Zn / Mo bimetallic aqueous ethanol solution. (2) Zn / Mo bimetallic doped ethanol aqueous solution was added dropwise to titanium sol precursor solution, aged, stood, dried, calcined and cooled to obtain Zn / Mo co-doped TiO2 nanofunctional powder without surface modification; (3) Zn / Mo co-doped TiO2 nanoparticles without surface modification were stirred at low speed under vacuum conditions; titanate coupling agent was added, and the mixture was heated and stirred to obtain Zn / Mo co-doped TiO2 nanoparticles.

[0010] In one embodiment, the melting temperature is 200~250°C.

[0011] In one embodiment, the molar ratio of titanium, zinc and molybdenum in step (1) is 100:1~2:1~2; the molar ratio of tetrabutyl titanate to anhydrous ethanol is 1:4~5. In step (1), the pH of the Zn / Mo bimetallic ethanol aqueous solution is adjusted to 3~3.5.

[0012] In one embodiment, after tetrabutyl titanate is mixed with anhydrous ethanol in step (1), it is stirred at 300-500 rpm for 20-40 min at 20-25°C.

[0013] In one embodiment, the dropping rate in step (2) is 1.5~3 mL / min; the calcination is carried out at a heating rate of 4~8℃ / min to 500~550℃, and then calcined at a constant temperature for 3~4 h.

[0014] In one embodiment, in step (2), aging is carried out at 50~60℃ for 12~14 h, standing is carried out at room temperature (20~25℃) for 24~30 h, and drying is carried out at 80~90℃ for 20~24 h.

[0015] In one embodiment, the amount of titanate coupling agent added in step (3) is 1.0~1.4% w / w of the unmodified Zn / Mo co-doped TiO2 nanoparticles.

[0016] In one embodiment, in step (3), low-speed stirring is stirring at 400~600 rpm for 30~40 min; heating stirring is heating to 120~150℃ and stirring at 3000~4000 rpm for 30~40 min.

[0017] A second objective of the present invention is to provide a photoresponsive antibacterial and UV-resistant polyester masterbatch prepared by any of the methods described above.

[0018] A third objective of the present invention is to provide a functional fiber obtained by spinning the aforementioned masterbatch.

[0019] A fourth objective of this invention is to provide the application of the above-mentioned photoresponsive antibacterial and UV-resistant polyester masterbatch in the textile field.

[0020] The fifth objective of this invention is to provide a method for simultaneously improving the photoresponsive antibacterial and UV-resistant properties of polyester masterbatch by adding Zn / Mo co-doped TiO2 nanoparticles. The preparation method of the Zn / Mo co-doped TiO2 nanopowder includes the following steps: (1) Tetrabutyl titanate was mixed with anhydrous ethanol under a nitrogen atmosphere to obtain a titanium sol precursor solution; Zinc nitrate hexahydrate and ammonium molybdate heptahydrate are dissolved in an aqueous ethanol solution and mixed to obtain a Zn / Mo bimetallic aqueous ethanol solution. (2) Zn / Mo bimetallic doped ethanol aqueous solution was added dropwise to titanium sol precursor solution, aged, stood, dried, calcined and cooled to obtain Zn / Mo co-doped TiO2 nanofunctional powder without surface modification; (3) Zn / Mo co-doped TiO2 nanoparticles without surface modification were stirred at low speed under vacuum conditions; titanate coupling agent was added, and the mixture was heated and stirred to obtain Zn / Mo co-doped TiO2 nanoparticles.

[0021] In one embodiment, the molar ratio of titanium, zinc and molybdenum in step (1) is 100:1~2:1~2; the molar ratio of tetrabutyl titanate to anhydrous ethanol is 1:4~5. In step (1), the pH of the Zn / Mo bimetallic ethanol aqueous solution is adjusted to 3~3.5.

[0022] In one embodiment, after tetrabutyl titanate is mixed with anhydrous ethanol in step (1), it is stirred at 300-500 rpm for 20-40 min at 20-25°C.

[0023] In one embodiment, the dropping rate in step (2) is 1.5~3 mL / min; the calcination is carried out at a heating rate of 4~8℃ / min to 500~550℃, and then calcined at a constant temperature for 3~4 h.

[0024] In one embodiment, in step (2), aging is carried out at 50℃~60℃ for 12~14 h, standing is carried out at room temperature (20~25℃) for 24~30 h, and drying is carried out at 80~90℃ for 20~24 h.

[0025] In one embodiment, the amount of titanate coupling agent added in step (3) is 1.0~1.4% w / w of the mass of the unmodified Zn / Mo co-doped TiO2 nanoparticles.

[0026] In one embodiment, in step (3), low-speed stirring is stirring at 400~600 rpm for 30~40 min; heating stirring is heating to 120~150℃ and stirring at 3000~4000 rpm for 30~40 min.

[0027] Beneficial effects of the present invention 1. This invention provides a method for preparing a Zn / Mo bimetallic synergistic TiO2 co-doping system and a unique powder surface modification technique. By controlling specific elemental ratios, precise preparation process parameters, and innovative surface treatment methods, a multifunctional nanopowder with both highly efficient photoresponsive antibacterial properties and full-band UV resistance is obtained. Based on this, the multifunctional nanopowder is combined with polyester to form a masterbatch for further processing.

[0028] Specifically, the polyester sample prepared by the present invention has an inhibition rate of >99.9% against Escherichia coli and Staphylococcus aureus under normal light conditions; the prepared polyester film (50μm) has a shielding rate of over 99.5% against UVA and UVB when the haze is only 0.9%, and the amount of titanate coupling agent used is significantly reduced (50%) during the preparation process.

[0029] 2. The polyester composite material provided by this invention achieves uniform nanoscale dispersion of Zn / Mo bimetallic synergistic TiO2 multifunctional nanoparticles within the polyester matrix, effectively avoiding powder agglomeration and mechanical property degradation. Simultaneously, the synergistic effect of EAA and MAH-g-POE further enhances the interfacial bonding between the powder and the matrix. Therefore, the composite material of this invention imparts excellent UV resistance and antibacterial properties to the matrix while significantly improving or maintaining its mechanical properties. Detailed Implementation

[0030] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explanation of the present invention and are not intended to limit the present invention.

[0031] In existing methods, conventional powder surface modification is usually completed by high-speed mixers under normal pressure or slight negative pressure. This invention, under the combination of high vacuum, high temperature and high speed kneading, can effectively remove trace amounts of moisture and alcohols from the powder surface and reaction byproducts, which greatly promotes the irreversible chemical bonding between titanate coupling agent and hydroxyl groups on the surface of nanoparticles, thereby achieving lower coupling agent dosage and better interfacial compatibility. In one embodiment of the present invention, during the surface modification process, the powder is first stirred at low speed to remove the moisture and air physically adsorbed on the powder surface; then the temperature of the material inside the cavity is further increased to make the powder in a highly fluidized and dispersed state.

[0032] Raw materials used in the examples: Polyester: Commercially available; Titanate coupling agent NDZ-105, CAS No.: 136144-62-2; Zinc nitrate hexahydrate, ammonium molybdate heptahydrate, tetrabutyl titanate, and anhydrous ethanol are all commercially available with a purity of ≥99.0%.

[0033] Test method: 1. Antibacterial properties: Refer to GB / T 31402-2015 "Test Method for Antibacterial Properties of Plastic Surfaces" (equivalent to ISO 22196:2011); Test strain: Staphylococcus aureus ( Staphylococcus aureus ATCC 6538) and Escherichia coli ( Escherichia coli (ATCC 8739) The masterbatch was then injection molded into 50mm×50mm sample pieces, and the bacterial suspension (10) was added. 10 CFU / mL was inoculated onto the sample surface, covered with a thin film, and exposed to visible light (simulated fluorescent lamp, light intensity 3000 lx) for 24 hours at 37℃ and humidity >90%.

[0034] 2. UV protection properties: The test was conducted using a UV-Vis spectrophotometer with an integrating sphere (PerkinElmer Lambda 950) based on the principle of GB / T 2410-2008 "Test Method for Transmittance and Haze of Transparent Plastics".

[0035] The masterbatch was then injection molded into a film with a thickness of 50 μm, and the spectral transmittance of the film in the wavelength range of 200-400 nm was tested. Ultraviolet shielding rate (%) = ( - average transmittance) × 100%.

[0036] 2. Tensile strength The tensile strength of the masterbatch was determined in accordance with the national standard GB / T 1040.1-2025 "Determination of tensile properties of plastics".

[0037] Example 1 1. A method for preparing Zn / Mo co-doped TiO2 functional nanoparticles, comprising the following steps: (1) Preparation of titanium sol precursor and Zn / Mo bimetallic ethanol aqueous solution Under a nitrogen atmosphere, 170.16 g (0.5 mol) of tetrabutyl titanate and 115.2 g (2.5 mol) of anhydrous ethanol were stirred at 500 rpm for 20 min at 25 °C until homogeneous to obtain a titanium sol precursor solution. 230.4 g (5.0 mol) of anhydrous ethanol and 54.0 g (3.0 mol) of deionized water were mixed to obtain an ethanol aqueous solution; 3.067 g (equivalent to 0.01031 mol of Zn) of zinc nitrate hexahydrate and 0.909 g of ammonium molybdate heptahydrate (equivalent to 0.00515 mol of Mo) were added, mixed thoroughly, and the pH was adjusted to 3.0 to obtain a Zn / Mo bimetallic ethanol aqueous solution; (2) Preparation of Zn / Mo-TiO2 nanopowders without surface modification A Zn / Mo bimetallic ethanol aqueous solution was added dropwise to a titanium sol precursor solution (25℃, 500 rpm) at a dropping rate of 2 mL / min. After the addition was completed, the solution was heated to 60℃ and aged for 12 h, then allowed to stand at room temperature (20~25℃) for 24 h. After standing, the solution was dried at 80℃ for 24 h, heated to 550℃ at a heating rate of 5℃ / min, and calcined at 550℃ for 3 h. After cooling, unmodified Zn / Mo co-doped TiO2 nanoparticles were obtained. (3) Preparation of Zn / Mo-TiO2 nanofunctional powder by surface modification Take 1000 g of Zn / Mo-TiO2 nanofunctional powder and put it into the kneader chamber. The vacuum degree inside the chamber is evacuated to below 0.1 Pa, and the mixture is stirred at 500 rpm for 30 min. Add 12 g of titanate coupling agent NDZ-105 and then heat to 135℃. Stir at 3500 rpm and keep the mixture at this temperature for 20 min. Cool to room temperature (20~25℃) to obtain surface-modified Zn / Mo-TiO2 nanofunctional powder.

[0038] The prepared surface-modified Zn / Mo-TiO2 nanoparticles have a particle size of 80.3 nm.

[0039] 2. Preparation of masterbatch Surface-modified Zn / Mo-TiO2 nanoparticles were thoroughly and uniformly mixed with dried polyester matrix, ethylene-acrylic acid copolymer, and maleic anhydride graft at a mass ratio of 5:100:1:1, melted at 225℃, extruded, and pelletized to prepare masterbatch.

[0040] Comparative Example 1 Based on Example 1, in step (1), ammonium molybdate heptahydrate and zinc nitrate hexahydrate are not added, and the amount of Ti added is kept consistent with the total amount of Zn, Mo and Ti added in Example 1, so as to prepare surface-modified TiO2 nanofunctional powder.

[0041] Comparative Example 2 Based on Example 1, in step (1), ammonium molybdate heptahydrate is not added, and the amount of Zn added is kept consistent with the total amount of Zn and Mo added in Example 1, so as to prepare surface-modified Zn-TiO2 nanofunctional powder.

[0042] Comparative Example 3 Based on Example 1, in step (1), zinc nitrate hexahydrate is not added, and the amount of Mo added is kept consistent with the total amount of Zn and Mo added in Example 1, so as to prepare surface-modified Mo-TiO2 nanofunctional powder.

[0043] Comparative Example 4 Based on Example 1, step (3) is changed as follows: Take 1000 g of Zn / Mo-TiO2 nanofunctional powder, add 12 g of titanate coupling agent NDZ-105, then heat to 135℃ and stir at 3500 r / min for 20 min to obtain surface-modified Zn / Mo-TiO2 nanofunctional powder.

[0044] Comparative Example 5 Based on Example 1, step (3) is changed as follows: Take 1000 g of Zn / Mo-TiO2 nanofunctional powder and put it into the kneader chamber. The vacuum degree inside the chamber is evacuated to below 0.1 Pa, and the mixture is stirred at a low speed of 500 r / min for 30 min. Add 12 g of titanate coupling agent NDZ-105 and then heat to 135℃. Stir and keep the mixture at 1500 r / min for 20 min and then cool to room temperature (20~25℃) to obtain surface-modified Zn / Mo-TiO2 nanofunctional powder.

[0045] Comparative Example 6 Based on Example 1, step (3) is changed as follows: Take 1000 g of Zn / Mo-TiO2 nanofunctional powder and put it into the kneader chamber. The vacuum degree inside the chamber is evacuated to below 0.1 Pa, and the mixture is stirred at a low speed of 500 r / min for 30 min. Add 12 g of titanate coupling agent NDZ-105 and then heat to 100℃. Stir and keep the mixture at 3500 r / min for 20 min and then cool to room temperature (20~25℃) to obtain surface-modified Zn / Mo-TiO2 nanofunctional powder.

[0046] Comparative Example 7 Based on Example 1, step (3) is changed as follows: Take 1000 g of Zn / Mo-TiO2 nanofunctional powder and put it into the kneader chamber. The vacuum degree inside the chamber is evacuated to below 0.1 Pa, and the mixture is stirred at a low speed of 500 r / min for 30 min. Add 25 g of titanate coupling agent NDZ-105 and then heat to 100℃. Stir and keep the mixture at 1500 r / min for 20 min and then cool to room temperature (20~25℃) to obtain surface-modified Zn / Mo-TiO2 nanofunctional powder.

[0047] Example 2 The surface-modified Zn / Mo-TiO2 nanoparticles prepared in Example 1 and Comparative Examples 1-8 were used to prepare sample sheets (50mm×50mm) and thin films (50μm), respectively. Their antibacterial properties and ultraviolet shielding properties were tested, and the results are shown in Table 1.

[0048] Table 1 Antibacterial properties

[0049] The antibacterial performance test results showed that the Comparative Example 1 (pure TiO2) sample had almost no antibacterial activity under visible light irradiation; after introducing single Zn or Mo into Comparative Examples 2 and 3, the antibacterial performance was significantly improved but still lower than that of Example 1, confirming that there is a significant synergistic effect between Zn and Mo.

[0050] UV protection performance tests showed that the UV shielding efficiency (>99.5%) of the film prepared in Example 1 was significantly higher than that of Comparative Examples 1, 2, and 3. The mechanism of action is that Zn doping enhances the intrinsic absorption of the UVA band, and Mo doping broadens the absorption spectrum range. The two work together to achieve efficient UV protection across the entire spectrum through the localized surface plasmon resonance (LSPR) effect and physical shielding.

[0051] Comparing the experimental results of Example 1 with those of Comparative Examples 4-6, it can be seen that, under the same conditions of coupling agent dosage, the powder prepared by vacuum kneading process with specific temperature and rotation speed parameters has significantly better interfacial compatibility and dispersion stability than the control group.

[0052] Comparing Example 1 with Comparative Example 7, it was found that Example 1 only requires 1.2% w / w of coupling agent to achieve excellent dispersion (0.8% haze), which significantly reduces the amount of coupling agent used compared with Comparative Example 7 (conventional process). This indicates that the surface modification process of the present invention can reduce the amount of titanate coupling agent used by more than 50%, thereby effectively reducing production costs.

[0053] Example 3 A method for preparing antibacterial and UV-resistant polyester filaments includes the following steps: The masterbatch obtained in Example 1 and polyester chips were mixed at a mass ratio of 70:30, melt-spun at 280°C, drawn at 70°C with a draw ratio of 3.0, and then set at 180°C to obtain polyester fibers with a monofilament linear density of 1.8 dtex.

[0054] The polyester filament prepared using the polyester masterbatch from Example 2 exhibits a breaking strength of 3.88 cN / dtex. This indicates that the Zn / Mo-TiO2 nanoparticles have good dispersion uniformity in the polyester matrix, resulting in a low breakage rate during the spinning process.

[0055] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. A method for preparing photoresponsive antibacterial and UV-resistant polyester masterbatch, characterized in that, It was prepared from Zn / Mo co-doped TiO2 nanoparticles, and the preparation method is as follows: Polyester, Zn / Mo co-doped TiO2 nanoparticles, ethylene-acrylic acid copolymer, and maleic anhydride grafts were mixed in a mass ratio of 100:5~8:0.5~2:0.5~2, melted, extruded, and pelletized to obtain a photoresponsive antibacterial and UV-resistant polyester masterbatch. The method for preparing the Zn / Mo co-doped TiO2 nanopowder includes the following steps: (1) Tetrabutyl titanate was mixed with anhydrous ethanol under a nitrogen atmosphere to obtain a titanium sol precursor solution; Zinc nitrate hexahydrate and ammonium molybdate heptahydrate are dissolved in an aqueous ethanol solution and mixed to obtain a Zn / Mo bimetallic aqueous ethanol solution. (2) Zn / Mo bimetallic doped ethanol aqueous solution was added dropwise to titanium sol precursor solution, aged, stood, dried, calcined and cooled to obtain Zn / Mo co-doped TiO2 nanofunctional powder without surface modification; (3) Zn / Mo co-doped TiO2 nanoparticles without surface modification were stirred at low speed under vacuum conditions; titanate coupling agent was added, and the mixture was heated and stirred to obtain Zn / Mo co-doped TiO2 nanoparticles.

2. The method according to claim 1, characterized in that, The melting temperature is 200~250℃.

3. The method according to claim 1, characterized in that, In step (1), the molar ratio of titanium, zinc and molybdenum is 100:1~2:1~2; the molar ratio of tetrabutyl titanate to anhydrous ethanol is 1:4~5. In step (1), the pH of the Zn / Mo bimetallic ethanol aqueous solution is adjusted to 3~3.

5.

4. The method according to claim 1, characterized in that, In step (2), the dropping rate is 1.5~3 mL / min; the calcination is carried out at a heating rate of 4~8℃ / min to 500~550℃, and then calcined at a constant temperature for 3~4 h.

5. The method according to claim 1, characterized in that, In step (3), the amount of titanate coupling agent added is 1.0~1.4% w / w of the unmodified Zn / Mo co-doped TiO2 nanoparticles.

6. The method according to claim 1, characterized in that, In step (3), the low-speed stirring is 400~600 rpm for 30~40 min; the heating stirring is heated to 120~150℃ and stirred at 3000~4000 rpm for 30~40 min.

7. The photoresponsive antibacterial and UV-resistant polyester masterbatch prepared by the method according to any one of claims 1 to 6.

8. A functional fiber, characterized in that, It is obtained by spinning the masterbatch described in claim 7.

9. The application of the photoresponsive antibacterial and UV-resistant polyester masterbatch as described in claim 8 in the textile field.

10. A method for simultaneously improving the photoresponsive antibacterial and UV-resistant properties of polyester masterbatch, characterized in that, Add Zn / Mo co-doped TiO2 nanoparticles; The preparation method of the Zn / Mo co-doped TiO2 nanopowder includes the following steps: (1) Tetrabutyl titanate was mixed with anhydrous ethanol under a nitrogen atmosphere to obtain a titanium sol precursor solution; Zinc nitrate hexahydrate and ammonium molybdate heptahydrate are dissolved in an aqueous ethanol solution and mixed to obtain a Zn / Mo bimetallic aqueous ethanol solution. (2) Zn / Mo bimetallic doped ethanol aqueous solution was added dropwise to titanium sol precursor solution, aged, stood, dried, calcined and cooled to obtain Zn / Mo co-doped TiO2 nanofunctional powder without surface modification; (3) Zn / Mo co-doped TiO2 nanoparticles without surface modification were stirred at low speed under vacuum conditions; Add titanate coupling agent, heat and stir to obtain Zn / Mo co-doped TiO2 nanoparticles.

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