Photoresponsive active material, preparation method thereof and nano-silver antibacterial master batch

Abstract

The application belongs to the technical field of antibacterial technology, and discloses a kind of photoresponsive active material and its preparation method and a kind of nano silver antibacterial master batch, the preparation method of photoresponsive active material is: first using SIPM as surfactant, water-soluble silver salt as precursor, ascorbic acid as reducing agent, synthesis nano silver hydrosol, then sequentially remove unreacted raw materials, dry to obtain water-soluble nano silver powder, then PTA and EG are esterified, and then EG, SIPM and water-soluble nano silver powder are added for polymerization reaction, and the photoresponsive active material is obtained;Photoresponsive active material has excellent hydrophilicity and thermal stability;Its application is: using ECDP as base material, the aforementioned photoresponsive active material is used as additive to prepare nano silver antibacterial master batch.The photoresponsive active material of the application has strong hydrophilicity and high thermal stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of antibacterial technology, and relates to a light response active material, a preparation method thereof and a nano-silver antibacterial master batch. BACKGROUND

[0002] In the current antibacterial technology field, photodynamic antibacterial technology is attracting much attention due to its unique advantages. In the presence of molecular oxygen, the photosensitizer is excited by light, and the energy is transferred to the surrounding oxygen and water, thereby generating singlet oxygen (¹O2), superoxide radicals (O2 - ) and hydroxyl radicals (·OH) and other high active oxygen species. Since singlet oxygen and radicals cause non-specific cell damage, photodynamic antibacterial technology is also effective on drug-resistant strains, and multiple photosensitive effects do not cause new bacterial drug resistance. At the same time, the transient life cycle of active oxygen ensures the environmental friendliness of the photosensitizer. This antibacterial technology is effective on a variety of pathogens, including bacteria, viruses and fungi, and has no safety hazards when contacting human skin, so it has attracted widespread attention in many fields, especially in the field of textiles.

[0003] In the field of textiles, it is of great significance to endow textiles with photodynamic antibacterial properties. Currently, if the existing photodynamic antibacterial technology for textiles adopts a post-finishing method, it is difficult to maintain the durability of antibacterial properties. The functional components are usually added to the fiber body by using functional master batches in the form of melt spinning to achieve intrinsic functionality. Therefore, it is of great value to develop a photodynamic antibacterial master batch that can be used in textiles. In the mechanism of photodynamic antibacterial technology, after the antibacterial material is irradiated, it exchanges electrons with the nearby O2 and H2O to generate superoxide radicals (·O2 - ) and hydroxyl radicals (·OH) to attack bacterial cells. Therefore, the design of a photodynamic antibacterial master batch for textiles needs to meet a series of conditions: (1) the master batch contains light-responsive active materials to promote the generation of active radicals; (2) the master batch matrix needs to have a certain hydrophilicity and contain a certain benzene ring group to increase the contact rate with O2 and H2O in the air, increase the yield of superoxide radicals (·O2 - ) and hydroxyl radicals (·OH), and improve the compatibility with polyester; (3) the light-responsive active materials in the master batch need to have a certain hydrophilicity to increase the contact rate with O2 and H2O in the air, increase the yield of superoxide radicals (·O2 - ) and hydroxyl radicals (·OH); (4) the light-responsive active materials in the master batch also need to have a certain thermal stability, which can remain stable at a temperature of 240-280℃ during the preparation of the master batch and subsequent spinning application, without inactivation, decomposition or degradation.

[0004] However, existing light-responsive active materials are difficult to have excellent hydrophilicity and thermal stability. For example, document 1 (Photodiagnosis and Photodynamic Therapy, 2019, 25:7-16.) mentions that toluidine blue, as a commonly used artificial synthetic photosensitive material, has been widely used in photodynamic therapy because of its safety and effectiveness, but due to its tendency to form aggregates in solution, resulting in low singlet oxygen production, the focus of the study is on adding different amounts of surfactants to improve the aggregation problem of toluidine blue.

[0005] Document 2 (Molecules, 2020, 25(7):1745-1745.) points out that porphyrin has become one of the most commonly used photosensitive materials due to its high ROS production rate and easy chemical modification. However, most photosensitive materials with porphyrin structure have the problems of poor water solubility and poor stability, making it difficult to be used directly as a drug, and need to be chemically modified to improve its hydrophilicity.

[0006] Document 3 (Biomedicines, 2021, 9(6): 584.) shows that some natural photosensitive materials, such as curcumin, hypericin, riboflavin, and chlorophyllin, have poor chemical and physical stability, and are not resistant to light and heat. For example, the β-diketone structure of curcumin is prone to enolization, decomposition and oxidation under the action of heat. Although some synthetic porphyrins are more stable than natural products, certain specific structures or substituents may cause their thermal stability to decrease.

[0007] Document 4 (APL materials, 12(6): 061110.) studies the effect of different substituents on the photosensitive activity and stability of porphyrin, although the article does not directly test the thermal stability, but shows that certain water-soluble porphyrins (such as TPPS series with carboxyl or sulfonic acid groups) will change their aggregation state at high temperatures, which in turn affects their performance. This is because high temperature will promote the aggregation of porphyrin molecules (H- or J-aggregation), change their optical properties, and lead to a decrease in the ability to produce reactive oxygen species (ROS).

[0008] In summary, this difficult situation of simultaneously having excellent hydrophilicity and thermal stability seriously hinders the successful preparation of textile photodynamic antibacterial masterbatch that meets the above conditions. The existing technology needs to break through this bottleneck to promote the further development and application of textile photodynamic antibacterial masterbatch.

[0009] Therefore, it is necessary to develop a light-responsive active material, a preparation method thereof, and a nano-silver antibacterial masterbatch to solve the above problems, which is of great significance. SUMMARY

[0010] The application aims to solve the problems in the prior art and provide a light response active material, a preparation method thereof and a nano-silver antibacterial master batch.

[0011] To achieve the above-mentioned purposes, the application adopts the technical solutions as follows:

[0012] The preparation method of the light response active material comprises the following steps: performing esterification reaction on PTA (terephthalic acid) and EG (ethylene glycol), adding EG, SIPM (dimethyl isophthalate-5-sulfonate) and water-soluble nano-silver powder into the esterification reaction product to perform polymerization reaction, and obtaining the light response active material.

[0013] The preparation process of the water-soluble nano-silver powder comprises the following steps: synthesizing nano-silver hydrosol by using SIPM as a surfactant, water-soluble silver salt as a precursor and ascorbic acid as a reducing agent, and then removing unreacted raw materials and drying in sequence to obtain the water-soluble nano-silver powder.

[0014] The application adopts the chemical reduction method, uses monomer SIPM as a surfactant, water-soluble silver salt as a precursor and ascorbic acid as a reducing agent, which not only guarantees the successful synthesis of the nano-silver powder, but also enables the SIPM to adhere to the surface of the nano-silver powder to obtain the water-soluble nano-silver powder. In the subsequent polymerization reaction process, the SIPM adhering to the surface of the nano-silver powder can further react with the esterification reaction product of PTA and EG, SIPM and EG to generate an oligomer with excellent hydrophilicity and thermal stability, and then the light response active material with excellent hydrophilicity and thermal stability is obtained.

[0015] The reason why the application adds EG, SIPM and water-soluble nano-silver powder into the esterification reaction product of PTA and EG to perform polymerization reaction instead of directly performing polymerization reaction on PTA, EG, SIPM and water-soluble nano-silver powder is that PTA will react with EG to generate esterification reaction, SIPM will react with EG to generate ester exchange reaction, and if the three kinds of reaction monomers are simultaneously put in, PTA and SIPM will compete with EG to generate reaction, and it is difficult to control the speed of polymerization and the polymerization degree of each polymerization unit.

[0016] As a preferred technical solution:

[0017] The preparation method of the light response active material as described above, the molar ratio of PTA, the first added EG, the second added EG, SIPM and water-soluble nano-silver powder is 1:2.55-4.2:1.5-3:1-1.2:1-1.1, wherein the molar ratio of the water-soluble nano-silver powder is determined by the following method: dissolving the water-soluble nano-silver powder in acetonitrile to prepare a 10 μg / mL solution, filtering with a 0.22 μm filter membrane, using a micro-sampler to suck the solution and drop it on the sampling probe, and using mass spectrometry to determine the molecular weight.

[0018] A preparation method of a light-responsive active material as described above, the specific steps are as follows:

[0019] (a) After mixing PTA, EG, titanium glycolate and sodium acetate, stirring for 30-60 min, esterification reaction is carried out at 245-255℃ and ≤0.1 MPa until the water output reaches 90-98% of the theoretical water output;

[0020] (b) EG, SIPM and water-soluble nano-silver powder are added, and the purpose of adding EG in this step is to ensure that there is enough EG and SIPM to react in the reaction system;

[0021] (c) Reaction is carried out at 250-260℃ and 0.1 MPa for 15 min;

[0022] (d) Reaction is carried out at 260-280℃ and ≤0.1 MPa until the motor stirring power reaches 3kW, the reaction melt is poured out while hot, and after cooling and agglomerating, the powder is obtained. Light-responsive active material.

[0023] The preparation method of a light-responsive active material as described above, the addition amount of titanium glycolate is 6-10ppm of the total mass of the reaction raw materials (PTA, EG, SIPM and water-soluble nano-silver powder), and the addition amount of sodium acetate is 1-1.5wt% of the total mass of the reaction raw materials.

[0024] The preparation method of a light-responsive active material as described above, the synthesis steps of water-soluble nano-silver powder are as follows:

[0025] (a) SIPM is added to deionized water, and stirred at 60-80℃ and 200-250rpm to be clear and transparent;

[0026] (b) A water-soluble silver salt solution (i.e. AgNO3 solution) with a concentration of 0.1-0.15M is added, the temperature and stirring speed are kept unchanged, and stirring is continued for 30-40 min;

[0027] (c) Ascorbic acid is added, the temperature is kept unchanged, the stirring speed is increased to 400-450rpm, and then the reaction is carried out for 2-2.5h, the solution gradually changes from yellow to red-brown, and a nano-silver hydrosol is obtained, wherein the particle size of nano-silver in the nano-silver hydrosol is 6-12nm;

[0028] (d) The nano-silver hydrosol was purified by dialysis using a semi-permeable membrane (200 Da, to filter out substances with a molecular weight of less than 200). The deionized water was changed every 0.5 h initially, then every 2-3 h after the second time, for a total of 3 times. Finally, the dialysis was performed for 36 h to ensure complete SIPM dialysis. The dialyzed nano-silver hydrosol was then dried (first by rotary evaporation at 70 °C, then by placing it in a vacuum drying oven at 60 °C for 5 h) to obtain water-soluble nano-silver powder.

[0029] In the preparation method of the photoresponsive active material described above, the molar ratio of ascorbic acid to water-soluble silver salt is 2-1.8:1, and the molar ratio of SIPM to water-soluble silver salt is 6-8:1.

[0030] This invention also provides a photoresponsive active material, prepared using the method described above. The photoresponsive active material is dispersed in a layered solution of water and n-hexane, and is uniformly dispersed only in the aqueous layer, indicating excellent hydrophilicity. The zeta potential ζ of an aqueous solution of the photoresponsive active material at a concentration of 20 mg / L, a temperature of 25°C, and a pH of 8 is -43.5 to -44.5 mV. In DLVO theory, |ζ| > 30 mV indicates good electrostatic stability, indicating good electrostatic stability of the photoresponsive active material. The initial thermal decomposition temperature of the photoresponsive active material is 352-355°C, higher than the spinning temperatures of polyester, CDP (cationic dyeable polyester), ECDP (cationic dye easily dyeable polyester), and nylon, indicating excellent thermal stability of the photoresponsive active material.

[0031] The present invention also provides a nano-silver antibacterial masterbatch, the substrate being ECDP and the additive being a photoresponsive active material as described above.

[0032] As a preferred technical solution:

[0033] The nano-silver antibacterial masterbatch described above uses commercially available ECDP chips. The intrinsic viscosity of ECDP is 0.5-0.6 dL / g, and the melting point is 240-248℃.

[0034] The content of photoresponsive active materials in the nano-silver antibacterial masterbatch is 70-80 wt%;

[0035] The nano-silver antibacterial masterbatch showed an antibacterial rate of no more than 10% against Staphylococcus aureus, Escherichia coli, and Candida albicans under light-free conditions, an antibacterial rate of no more than 10% against drug-resistant MRSA under light-free conditions, and an antiviral rate of no more than 5% against N1H1 virus under light-free conditions.

[0036] The 3min antibacterial rates of the nano-silver antibacterial master batch on Staphylococcus aureus, Escherichia coli and Candida albicans under light conditions are all above 99.9%, the 3min antibacterial rate on drug-resistant bacteria MRSA under light conditions is above 99.9%, and the 3min antiviral rate on N1H1 virus under light conditions is above 99%.

[0037] Beneficial effects:

[0038] (1) The chemical reduction method adopted in the present application can not only guarantee the successful synthesis of nano-silver powder, but also enable SIPM to adhere to the surface of the nano-silver powder, and in the subsequent polymerization reaction process, the SIPM adhering to the surface of the nano-silver powder can further react with the esterification product of PTA and EG, SIPM and EG to generate an oligomer with excellent hydrophilicity and thermal stability, and then obtain a photoresponsive active material with excellent hydrophilicity and thermal stability; the photoresponsive active material of the present application has strong hydrophilicity of sulfonic acid group and high thermal stability of polyester backbone, so that the hydrophilicity and thermal stability are synergistically improved.

[0039] (2) The polyester-based structure of the photoresponsive active material of the present application has good compatibility with the polyester spinning matrix, meeting the requirements of textile processing.

[0040] (3) The present application first performs esterification reaction on PTA and EG, and then adds EG, SIPM and water-soluble nano-silver powder to perform polymerization reaction, so that the problem of competition reaction between PTA and SIPM and EG and the difficulty in controlling the degree of polymerization can be avoided.

[0041] (4) The photoresponsive active material of the present application is environmentally friendly and sustainable, the transient life cycle of active oxygen ensures the environmental friendliness of the material, and there is no antibiotic or heavy metal residue, which meets the safety standards of textiles; the photodynamic antibacterial mechanism does not cause bacterial resistance, providing a new idea for solving the problem of antibiotic abuse. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 It is a structure schematic diagram of the water-soluble nano-silver powder of the embodiment A1 of the present application;

[0043] Figure 2 It is an infrared spectrum diagram of the water-soluble nano-silver powder of the embodiment A1 of the present application;

[0044] Figure 3 It is a thermogravimetric curve diagram of the water-soluble nano-silver powder of the embodiment A1 of the present application;

[0045] Figure 4 It is a synthesis path diagram of the photoresponsive active material of the present application;

[0046] Figure 5NMR spectrum of the light-responsive active material of Example A2 of the present application;

[0047] Figure 6 NMR spectrum of the light-responsive active material of Example A5 of the present application 13 C-NMR spectrum. DETAILED DESCRIPTION

[0048] The present application will be further described in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application and not used to limit the scope of the present application. Furthermore, it should be understood that after reading the content taught by the present application, those skilled in the art can make various modifications or changes to the present application, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

[0049] In order to ensure that the properties of the substances used in each embodiment are fully disclosed, the manufacturers and brands of the substances are written, and other products of other manufacturers and brands that meet the definition of the present application are also feasible.

[0050] The test methods of the relevant performance indicators in the following examples and comparative examples are as follows:

[0051] Particle size of nano-silver in nano-silver aqueous sol: the nano-silver aqueous sol prepared in each example was used as a sample, then a small amount of sample was placed in a sample bottle and ultrasonically dispersed after being dropped on a copper grid supported by an ultrathin carbon film, dried and placed on a sample stage, finally the morphology and size of the nano-silver were microscopically analyzed by a transmission electron microscope (manufacturer: Japan JEOL Co., Ltd., model: JEM-2100), and statistical analysis was performed by Image J software to obtain the particle size of the nano-silver in the nano-silver aqueous sol.

[0052] Intrinsic viscosity: the sample was mixed uniformly in a phenol / tetrachloroethane mixed solution, then the intrinsic viscosity of the sample was measured at 25°C by an AVSPRO automatic viscosity meter; wherein the weight ratio of phenol / tetrachloroethane in the mixed solution was 1:1.

[0053] Initial thermal decomposition temperature of the light-responsive active material: the light-responsive active material prepared in each example was used as a sample, then the thermal gravimetric curve of the sample was tested by a NC88-TG 209 F1 Iris type thermal gravimetric analyzer in a nitrogen environment, the temperature at which the thermal gravimetric weight of the sample was 5wt% was the initial thermal decomposition temperature of the sample; wherein the temperature test interval was set to 40-800°C, and the temperature rising rate was 10°C·min -1 .

[0054] Zeta potential value of the aqueous solution of the light-responsive active material: the light-responsive active material prepared in each example was taken as a sample, respectively, and first dispersed into deionized water to obtain a mixed aqueous solution with a concentration of 20 mg / L, and then the pH value of the mixed solution was adjusted to 8 by using a 1 mol / L NaOH aqueous solution, and finally the zata potential value of the mixed solution was determined by using a ZS 90 nanoparticle size and potential analyzer of Malvern.

[0055] Antibacterial rate of the master batch against S. aureus, E. coli, C. albicans and drug-resistant bacteria MRSA: the master batch prepared in each example and the comparative example was taken as a sample, respectively, and then the antibacterial property under light and without light was tested according to the standard GB / T 31402-2015 “Plastics-Determination of antibacterial property of plastic surface”; wherein, the light condition was carried out according to the standard GB / T 30706-2014 “Test method and evaluation of antibacterial property of photocatalytic antibacterial materials and products under visible light irradiation”, and the specific light condition was as follows: LED lamp, color temperature 5000K, color rendering index 95%, wavelength distribution 380nm-780nm, and an ultraviolet cutoff filter was used to filter out ultraviolet light less than 400nm when in use.

[0056] Antiviral rate of the master batch against N1H1 virus: the master batch prepared in each example and the comparative example was taken as a sample, respectively, and then the antiviral test was carried out on the sample under light and without light according to the standard GB / T 43355-2023 “Determination of antiviral activity on the surface of plastics and other non-porous materials”; wherein, the light condition was carried out according to the standard GB / T 30706-2014 “Test method and evaluation of antibacterial property of photocatalytic antibacterial materials and products under visible light irradiation”, and the specific light condition was as follows: LED lamp, color temperature 5000K, color rendering index 95%, wavelength distribution 380nm-780nm, and an ultraviolet cutoff filter was used to filter out ultraviolet light less than 400nm when in use.

[0057] Example A1

[0058] A preparation method of a light-responsive active material, the synthesis path of which is shown in Figure 4 The steps are as follows:

[0059] (1) Preparation of water-soluble silver nanopowder;

[0060] (1.1) SIPM was added into deionized water, and stirred at 75℃ and a stirring speed of 200 rpm until clear and transparent; wherein, the molar ratio of SIPM to deionized water was 1:9.

[0061] (1.2) adding an aqueous solution of AgNO3 with a concentration of 0.1 M to the stirred solution of step (1.1), and then continuing to stir at the stirring temperature and stirring speed of step (1.1) for 35 min; wherein the molar ratio of SIPM to AgNO3 is 8:1;

[0062] (1.3) adding ascorbic acid to the stirred solution of step (1.2), and then reacting for 2.5 h after the stirring temperature of step (1.2) is reached and the stirring speed is increased to 420 rpm, during which the solution gradually changes from yellow to red-brown, to obtain a silver nanoparticle aqueous sol; wherein the average particle size of the silver nanoparticles in the silver nanoparticle aqueous sol is 6 nm, and the molar ratio of ascorbic acid to AgNO3 is 1.8:1;

[0063] (1.4) performing dialysis purification of the silver nanoparticle aqueous sol using a semi-permeable membrane with a MW of 200, initially replacing the deionized water every 0.5 h for 2 times, then every 2 h for 3 times, and finally dialyzing for 36 h, to ensure that the SIPM is completely dialyzed, and then the dialyzed silver nanoparticle aqueous sol is first rotary evaporated at 70℃, and then placed in a vacuum drying oven at 60℃ for 5 h, to obtain a water-soluble silver nanoparticle powder (the structure of which is shown in Figure 1 , the infrared spectrum of which is shown in Figure 2 , and the thermogravimetric curve of which is shown in Figure 3 );

[0064] (2) mixing PTA, EG, titanium glycolate, and sodium acetate, stirring for 30 min, and then performing esterification at 250℃ and 0.1 MPa until the water output reaches 92% of the theoretical water output; wherein the addition amount of titanium glycolate is 6 ppm of the total mass of the reaction raw materials, and the addition amount of sodium acetate is 1 wt% of the total mass of the reaction raw materials;

[0065] (3) adding EG, SIPM, and the water-soluble silver nanoparticle powder obtained in step (1) to the system of step (2);

[0066] In steps (2)-(3), the molar ratio of PTA, the EG added in step (2), the EG added in step (3), SIPM, and the water-soluble silver nanoparticle powder is 1:2.55:1.8:1.2:1;

[0067] (4) reacting at 255℃ and 0.1 MPa for 15 min;

[0068] (5) reacting at 265℃ and 0.1 MPa, and terminating the reaction when the motor stirring power reaches 3 kW, and then pouring out the reaction melt while hot, grinding the cooled and agglomerated product, to obtain a light-responsive active material, which is a modified polyester (a polyester composed of PTA segments, EG segments, and SIPM segments) in which part of the chain segments in the molecular chain are replaced by water-soluble silver nanoparticles.

[0069] The intrinsic viscosity of the prepared photoresponsive active material is 0.55 dL / g;

[0070] The prepared photoresponsive active material is dispersed in a layered solution of water and n-hexane, and the photoresponsive active material is uniformly dispersed only in the water layer;

[0071] The zeta potential value ζ of the photoresponsive active material aqueous solution with a concentration of 20 mg / L, a temperature of 25°C and a pH value of 8 is -43.5 mV;

[0072] The initial thermal decomposition temperature of the photoresponsive active material is 352°C.

[0073] Comparative Example A1

[0074] A method for preparing a photoresponsive active material, which is basically the same as in Example A1, except that step (1) is not performed, and the water-soluble nano-silver powder in step (3) is replaced with an equal amount of nano-silver powder prepared according to the present comparative example, wherein the preparation process of the nano-silver powder is as follows: using oleic acid and n-butylamine as surfactants, AgNO3 as a precursor, and ascorbic acid as a reducing agent, the nano-silver sol prepared by synthesis is precipitated in ethanol to obtain nano-silver powder with an average particle size of 6 nm;

[0075] The final photoresponsive active material cannot be dispersed in water, but only in organic solvents such as n-hexane; and the extrapolated initial thermal decomposition temperature of the material is 181°C.

[0076] Example A2

[0077] A method for preparing a photoresponsive active material, the steps of which are as follows:

[0078] (1) preparing water-soluble nano-silver powder;

[0079] (1.1) adding SIPM to deionized water and stirring at 60°C and a stirring speed of 230 rpm until it becomes clear and transparent; wherein the molar ratio of SIPM to deionized water is 1:8;

[0080] (1.2) adding an AgNO3 aqueous solution with a concentration of 0.11 M to the solution after stirring in step (1.1), and then continuing to stir at the stirring temperature and stirring speed in step (1.1) for 30 min; wherein the molar ratio of SIPM to AgNO3 is 7:1;

[0081] (1.3) adding ascorbic acid to the stirred solution of step (1.2), then increasing the stirring speed to 400 rpm at the stirring temperature of step (1.2), and then reacting for 2 h, during which the solution gradually changes from yellow to red-brown, to obtain a silver nanoparticle aqueous solution; wherein the average particle size of the silver nanoparticles in the silver nanoparticle aqueous solution is 7 nm, and the molar ratio of ascorbic acid to AgNO3 is 1.9:1;

[0082] (1.4) performing dialysis purification of the silver nanoparticle aqueous solution by using a semi-permeable membrane with a MW of 200, initially replacing the deionized water every 0.5 h for 2 times, then every 3 h for 3 times, and finally dialyzing for 36 h after ensuring that the SIPM is completely dialyzed, and then performing rotary evaporation at 70 ℃, and then placing the dialyzed silver nanoparticle aqueous solution in a vacuum drying box at 60 ℃ for 5 h to obtain a water-soluble silver nanoparticle powder;

[0083] (2) mixing PTA, EG, titanium glycolate, and sodium acetate, stirring for 60 min, and then performing esterification at 245 ℃ and 0.099 MPa until the water output reaches 90% of the theoretical water output; wherein the addition amount of titanium glycolate is 7 ppm of the total mass of the reaction raw materials, and the addition amount of sodium acetate is 1.5 wt% of the total mass of the reaction raw materials;

[0084] (3) adding EG, SIPM, and the water-soluble silver nanoparticle powder obtained in step (1) to the system of step (2);

[0085] In steps (2)-(3), the molar ratio of PTA, the EG added in step (2), the EG added in step (3), SIPM, and the water-soluble silver nanoparticle powder is 1:3.1:2:1.1:1;

[0086] (4) reacting at 250 ℃ and 0.1 MPa for 15 min;

[0087] (5) reacting at 260 ℃ and 0.099 MPa, and terminating the reaction when the motor stirring power reaches 3 kW, and then pouring out the reaction melt while hot, grinding the cooled mass, and obtaining a photoresponsive active material (the 1H-NMR spectrum of which is shown in FIG. 1). Figure 5

[0088] The inherent viscosity of the photoresponsive active material prepared above is 0.58 dL / g;

[0089] The photoresponsive active material prepared above is dispersed in a layered solution of water and n-hexane, and the photoresponsive active material is uniformly dispersed only in the water layer;

[0090] The zeta potential value ζ of a water solution of the photoresponsive active material with a concentration of 20 mg / L, a temperature of 25 ℃, and a pH value of 8 is -44.0 mV; ​

[0091] The initial thermal decomposition temperature of the photoresponsive active material is 353°C.

[0092] Example A3

[0093] A preparation method of a photoresponsive active material, comprising the following steps:

[0094] (1) preparing water-soluble nano-silver powder;

[0095] (1.1) adding SIPM into deionized water, and stirring at 80°C and a stirring speed of 250 rpm until the solution is clear and transparent; wherein the molar ratio of SIPM to deionized water is 1:10;

[0096] (1.2) adding an aqueous solution of AgNO3 with a concentration of 0.12M into the solution after stirring in step (1.1), and then continuing to stir at the stirring temperature and stirring speed in step (1.1) for 40 min; wherein the molar ratio of SIPM to AgNO3 is 6:1;

[0097] (1.3) adding ascorbic acid into the solution after stirring in step (1.2), and then increasing the stirring speed to 450 rpm while maintaining the stirring temperature in step (1.2), and then reacting for 2.5 h, during which the solution gradually changes from yellow to red-brown, to obtain a nano-silver hydrosol; wherein the average particle size of nano-silver in the nano-silver hydrosol is 12 nm, and the molar ratio of ascorbic acid to AgNO3 is 2:1;

[0098] (1.4) performing dialysis purification on the nano-silver hydrosol by using a semi-permeable membrane with a MW of 200, and changing the deionized water every 0.5 h for the first two times, then changing the water every 2 h for the next three times, and finally dialyzing for 36 h; after ensuring that the SIPM is completely dialyzed, the nano-silver hydrosol after dialysis is first rotary evaporated at 70°C, and then placed in a vacuum drying box at 60°C for 5 h, to obtain water-soluble nano-silver powder;

[0099] (2) mixing PTA, EG, titanium glycolate, and sodium acetate, stirring for 60 min, and then performing esterification under the conditions of 255°C and 0.099 MPa until the water output reaches 98% of the theoretical water output; wherein the addition amount of titanium glycolate is 8 ppm of the total mass of the reaction raw materials, and the addition amount of sodium acetate is 1.2 wt% of the total mass of the reaction raw materials;

[0100] (3) adding EG, SIPM, and the water-soluble nano-silver powder obtained in step (1) into the system in step (2);

[0101] In steps (2)-(3), the molar ratio of PTA, EG added in step (2), EG added in step (3), SIPM, and water-soluble nano-silver powder is 1:4.2:3:1:1.1;

[0102] (4) reacting at 260℃, 0.1 MPa for 15 min;

[0103] (5) reacting at 280℃, 0.099 MPa, and stopping the reaction when the motor stirring power reaches 3 kW, then pouring out the reaction melt while hot, grinding the solidified mass into powder, and obtaining the photoresponsive active material.

[0104] The photoresponsive active material prepared above has an intrinsic viscosity of 0.65 dL / g;

[0105] The photoresponsive active material prepared above is dispersed into a layered solution of water and n-hexane, and the photoresponsive active material is uniformly dispersed only in the water layer;

[0106] The zeta potential value ζ of an aqueous solution of the photoresponsive active material with a concentration of 20 mg / L, a temperature of 25℃, and a pH value of 8 is -43.7 mV;

[0107] The photoresponsive active material has an initial thermal decomposition temperature of 355℃.

[0108] Example A4

[0109] A method for preparing a photoresponsive active material, comprising the following steps:

[0110] (1) preparing a water-soluble nano-silver powder;

[0111] (1.1) adding SIPM into deionized water, and stirring at 70℃ and a stirring speed of 230 rpm until the solution is clear and transparent; wherein the molar ratio of SIPM to deionized water is 1:9;

[0112] (1.2) adding an aqueous solution of AgNO3 with a concentration of 0.13 M into the solution after stirring in step (1.1), and then continuing to stir at the stirring temperature and stirring speed in step (1.1) for 35 min; wherein the molar ratio of SIPM to AgNO3 is 7:1;

[0113] (1.3) adding ascorbic acid into the solution after stirring in step (1.2), and then increasing the stirring speed to 420 rpm while maintaining the stirring temperature in step (1.2), and reacting for 2 h, during which the solution gradually changes from yellow to red-brown, to obtain a nano-silver hydrosol; wherein the average particle size of nano-silver in the nano-silver hydrosol is 8 nm, and the molar ratio of ascorbic acid to AgNO3 is 1.9:1;

[0114] (1.4) The nanosilver water sol is purified by dialysis with a semi-permeable membrane of MW200, and the deionized water is changed every 0.5 h initially, and then every 3 h for 3 times after 2 times, and finally the dialysis is performed for 36 h. After ensuring that the SIPM is completely dialyzed, the nanosilver water sol after dialysis is first rotary evaporated at 70 ℃, and then placed in a vacuum drying box at 60 ℃ for 5 h to obtain a water-soluble nanosilver powder;

[0115] (2) The PTA, EG, titanium glycolate and sodium acetate are mixed, stirred for 40 min, and then subjected to esterification at 248 ℃ and 0.099 MPa until the water output reaches 94% of the theoretical water output; wherein the addition amount of the titanium glycolate is 9 ppm of the total mass of the reaction raw materials, and the addition amount of the sodium acetate is 1.1 wt% of the total mass of the reaction raw materials;

[0116] (3) The EG, SIPM and the water-soluble nanosilver powder obtained in step (1) are added to the system of step (2);

[0117] In steps (2)-(3), the molar ratio of PTA, EG added in step (2), EG added in step (3), SIPM and water-soluble nanosilver powder is 1:2.55:2:1.2:1.1;

[0118] (4) The reaction is performed at 250 ℃ and 0.1 MPa for 15 min;

[0119] (5) The reaction is performed at 270 ℃ and 0.098 MPa, and the reaction is terminated when the motor stirring power reaches 3 kW, then the reaction melt is poured out while hot, and the powder is obtained after cooling and agglomeration, to obtain a light-responsive active material.

[0120] The intrinsic viscosity of the light-responsive active material prepared above is 0.56 dL / g;

[0121] The light-responsive active material prepared above is dispersed into a layered solution of water and n-hexane, and the light-responsive active material is uniformly dispersed only in the water layer;

[0122] The zeta potential value ζ of the aqueous solution of the light-responsive active material with a concentration of 20 mg / L, a temperature of 25 ℃ and a pH value of 8 is -44.5 mV;

[0123] The initial thermal decomposition temperature of the light-responsive active material is 354 ℃.

[0124] Example A5

[0125] A method for preparing a light-responsive active material, the steps are as follows:

[0126] (1) Preparation of a water-soluble nanosilver powder;

[0127] (1.1) add SIPM into deionized water, and stir at 75℃ and a stirring speed of 230 rpm until clear and transparent; wherein the molar ratio of SIPM to deionized water is 1:9;

[0128] (1.2) add an aqueous solution of AgNO3 with a concentration of 0.14 M into the solution after stirring in step (1.1), and then continue stirring at the stirring temperature and stirring speed in step (1.1) for 35 min; wherein the molar ratio of SIPM to AgNO3 is 8:1;

[0129] (1.3) add ascorbic acid into the solution after stirring in step (1.2), and then increase the stirring speed to 420 rpm after stirring at the stirring temperature in step (1.2), and react for 2.5 h, during which the solution gradually changes from yellow to red-brown, to obtain a nano-silver aqueous sol; wherein the average particle size of nano-silver in the nano-silver aqueous sol is 9 nm, and the molar ratio of ascorbic acid to AgNO3 is 1.8:1;

[0130] (1.4) perform dialysis purification of the nano-silver aqueous sol by using a semi-permeable membrane with MW200, and change deionized water every 0.5 h for the first two times, then change water every 2 h for the next three times, and finally dialyze for 36 h, and after ensuring that SIPM is completely dialyzed, the nano-silver aqueous sol after dialysis is first rotary evaporated at 70℃, and then placed in a vacuum drying box at 60℃ for 5 h to obtain a water-soluble nano-silver powder;

[0131] (2) mix PTA, EG, titanium glycolate and sodium acetate, stir for 60 min, and then perform esterification under the conditions of 252℃ and 0.099 MPa until the water output reaches 96% of the theoretical water output; wherein the addition amount of titanium glycolate is 6 ppm of the total mass of reaction raw materials, and the addition amount of sodium acetate is 1.3 wt% of the total mass of reaction raw materials;

[0132] (3) add EG, SIPM and the water-soluble nano-silver powder obtained in step (1) into the system in step (2);

[0133] In steps (2)-(3), the molar ratio of PTA, EG added in step (2), EG added in step (3), SIPM and the water-soluble nano-silver powder is 1:2.8:2:1:1.1;

[0134] (4) react under the conditions of 255℃ and 0.1 MPa for 15 min;

[0135] (5) react under the conditions of 275℃ and 0.099 MPa, and terminate the reaction when the motor stirring power reaches 3 kW, then pour out the reaction melt while hot, grind the cooled and agglomerated product into powder, and obtain a light-responsive active material (the 1H-NMR spectrum of which is shown in FIG. 1, and the 13C-NMR spectrum of which is shown in FIG. 2); 13 C-NMR spectrum is shown in FIG. 2.Figure 6 (As shown).

[0136] The intrinsic viscosity of the photoresponsive active material prepared above is 0.60 dL / g;

[0137] The photoresponsive active material prepared above was dispersed in a layered solution of water and n-hexane, and the photoresponsive active material was uniformly dispersed only in the water layer.

[0138] The zeta potential ζ of an aqueous solution of a photoresponsive material with a concentration of 20 mg / L, a temperature of 25 °C, and a pH of 8 is -44.2 mV.

[0139] The initial thermal decomposition temperature of the photoresponsive material is 352℃.

[0140] Example A6

[0141] A method for preparing a photoresponsive active material, comprising the following steps:

[0142] (1) Preparation of water-soluble nano-silver powder;

[0143] (1.1) Add SIPM to deionized water and stir at 220 rpm at 70°C until clear and transparent; wherein the molar ratio of SIPM to deionized water is 1:9;

[0144] (1.2) Add a 0.15M aqueous solution of AgNO3 to the solution after stirring in step (1.1), and then continue stirring for 35 minutes at the stirring temperature and stirring speed in step (1.1); wherein the molar ratio of SIPM to AgNO3 is 8:1.

[0145] (1.3) Add ascorbic acid to the solution after stirring in step (1.2), and then increase the stirring speed to 420 rpm at the stirring temperature in step (1.2) and react for 2 hours. The solution gradually changes from yellow to reddish-brown to obtain nano-silver hydrosol. The average particle size of the nano-silver in the nano-silver hydrosol is 10 nm, and the molar ratio of ascorbic acid to AgNO3 is 1.8:1.

[0146] (1.4) The nano-silver hydrosol was purified by dialysis using a MW200 semi-permeable membrane. Initially, the deionized water was changed every 0.5 h, then every 3 h for the next two times, for a total of three times. Finally, the dialysis was performed for 36 h to ensure complete SIPM dialysis. After the dialysis, the nano-silver hydrosol was first evaporated by rotary evaporation at 70 °C, and then placed in a vacuum drying oven at 60 °C for 5 h to obtain water-soluble nano-silver powder.

[0147] (2) mixing PTA, EG, titanium glycol, and sodium acetate, stirring for 50 min, and then performing esterification reaction at 254℃ and 0.099 MPa until the water output reaches 96% of the theoretical water output; wherein the addition amount of titanium glycol is 10 ppm of the total mass of the reaction raw materials, and the addition amount of sodium acetate is 1.4 wt% of the total mass of the reaction raw materials;

[0148] (3) adding EG, SIPM, and the water-soluble nano-silver powder obtained in step (1) to the system of step (2);

[0149] In steps (2)-(3), the molar ratio of PTA, EG added in step (2), EG added in step (3), SIPM, and the water-soluble nano-silver powder is 1:4.0:1.5:1.2:1;

[0150] (4) performing reaction at 255℃ and 0.1 MPa for 15 min;

[0151] (5) performing reaction at 280℃ and 0.1 MPa, and terminating the reaction when the motor stirring power reaches 3 kW, then pouring out the reaction melt while hot, grinding the solidified mass after cooling, and obtaining the light-responsive active material.

[0152] The intrinsic viscosity of the light-responsive active material prepared above is 0.62 dL / g;

[0153] Dispersing the light-responsive active material prepared above into a layered solution of water and n-hexane, and the light-responsive active material is uniformly dispersed only in the water layer;

[0154] The zeta potential value ζ of the aqueous solution of the light-responsive active material with a concentration of 20 mg / L, a temperature of 25℃, and a pH value of 8 is -43.6 mV;

[0155] The initial thermal decomposition temperature of the light-responsive active material is 353℃.

[0156] Example B1

[0157] A preparation method of a nano-silver antibacterial master batch, and the specific process is as follows:

[0158] A nano-silver antibacterial master batch was prepared by blending ECDP (intrinsic viscosity of 0.58 dL / g, melting point of 246°C) as a base material and the light-responsive active material prepared in Example A1 as an additive, and then extruding and granulating in a twin-screw extruder. In the nano-silver antibacterial master batch, the content of the light-responsive active material was 70 wt%, and the process parameters of the twin-screw extruder during preparation were as follows: the temperature of heating zone I was 235°C, the temperature of heating zone II was 245°C, the temperature of heating zone III was 255°C, the temperature of heating zone IV was 260°C, the temperature of heating zone V was 260°C, the temperature of the die head was 255°C, the rotation speed of the main machine was 36 rpm, and the rotation speed of the feeding machine was 15 rpm.

[0159] The prepared nano-silver antibacterial master batch had 3 min antibacterial rates of 8%, 6%, and 5% against Staphylococcus aureus, Escherichia coli, and Candida albicans, respectively, under non-illumination conditions, a 3 min antibacterial rate of 8% against drug-resistant bacteria MRSA under non-illumination conditions, and a 3 min antiviral rate of 2% against N1H1 virus under non-illumination conditions.

[0160] The nano-silver antibacterial master batch had 3 min antibacterial rates of 99.9%, 99.9%, and 99.9% against Staphylococcus aureus, Escherichia coli, and Candida albicans, respectively, under illumination conditions, a 3 min antibacterial rate of 99.9% against drug-resistant bacteria MRSA under illumination conditions, and a 3 min antiviral rate of 99.9% against N1H1 virus under illumination conditions.

[0161] Comparative Example B1

[0162] A method for preparing a nano-silver master batch was basically the same as in Example B1, except that ECDP was replaced by PET (intrinsic viscosity of 0.68 dl / g, melting point of 265°C) with the same mass.

[0163] The prepared nano-silver master batch had 3 min antibacterial rates of 0%, 0%, and 0% against Staphylococcus aureus, Escherichia coli, and Candida albicans, respectively, under non-illumination conditions, a 3 min antibacterial rate of 0% against drug-resistant bacteria MRSA under non-illumination conditions, and a 3 min antiviral rate of 0% against N1H1 virus under non-illumination conditions.

[0164] The nano-silver master batch had 3 min antibacterial rates of 0%, 0%, and 0% against Staphylococcus aureus, Escherichia coli, and Candida albicans, respectively, under illumination conditions, a 3 min antibacterial rate of 0% against drug-resistant bacteria MRSA under illumination conditions, and a 3 min antiviral rate of 0% against N1H1 virus under illumination conditions.

[0165] Comparative Example B1 and Example B1 can be compared, the antibacterial and antiviral properties of the nano-silver masterbatch prepared in the comparative example decreased significantly, because the matrix for preparing the nano-silver antibacterial masterbatch in the comparative example does not have hydrophilicity, the contact rate with O2 and H2O in the air in a short time is low, the production of superoxide free radicals (·O2 - ) and hydroxyl radicals (·OH) generated by light is low, so it almost does not show light antibacterial property.

[0166] Comparative Example B2

[0167] A method for preparing a nano-silver masterbatch, which is basically the same as Example B1, except that the light-responsive active material used is prepared from Comparative Example A1.

[0168] The nano-silver masterbatch prepared has 3 min antibacterial rates of 0%, 0%, and 0% against Staphylococcus aureus, Escherichia coli, and Candida albicans respectively under non-illumination conditions, a 3 min antibacterial rate of 0% against drug-resistant bacteria MRSA under non-illumination conditions, and a 3 min antiviral rate of 0% against N1H1 virus under non-illumination conditions;

[0169] The nano-silver masterbatch has 3 min antibacterial rates of 0%, 0%, and 0% against Staphylococcus aureus, Escherichia coli, and Candida albicans respectively under illumination conditions, a 3 min antibacterial rate of 0% against drug-resistant bacteria MRSA under illumination conditions, and a 3 min antiviral rate of 0% against N1H1 virus under illumination conditions.

[0170] Example B2

[0171] A method for preparing a nano-silver antibacterial masterbatch, the specific process is as follows:

[0172] ECDP (intrinsic viscosity of 0.5 dL / g, melting point of 240°C) as a base material, and the light-responsive active material prepared in Example A2 as an additive, the two were blended and then added to a twin-screw extruder for extrusion granulation to obtain a nano-silver antibacterial masterbatch; wherein the content of the light-responsive active material in the nano-silver antibacterial masterbatch is 80 wt%, and the process parameters of the twin-screw extruder during preparation are as follows: heating I zone temperature is 235°C, heating II zone temperature is 245°C, heating III zone temperature is 255°C, heating IV zone temperature is 260°C, heating V zone temperature is 260°C, die temperature is 255°C, main machine speed is 36 rpm, and feeding speed is 15 rpm.

[0173] The nano-silver antibacterial masterbatch prepared has 3 min antibacterial rates of 7%, 7%, and 7% against Staphylococcus aureus, Escherichia coli, and Candida albicans respectively under non-illumination conditions, a 3 min antibacterial rate of 7% against drug-resistant bacteria MRSA under non-illumination conditions, and a 3 min antiviral rate of 3% against N1H1 virus under non-illumination conditions;

[0174] The 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on Staphylococcus aureus, Escherichia coli and Candida albicans is 99.9%, 99.9% and 99.9% respectively, the 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on drug-resistant bacteria MRSA is 99.9%, and the 3 min antiviral rate of the nano-silver antibacterial master batch under light conditions on N1H1 virus is 99.9%.

[0175] Example B3

[0176] A preparation method of a nano-silver antibacterial master batch, the specific process is as follows:

[0177] ECDP (intrinsic viscosity of 0.6 dL / g, melting point of 248℃) as a base material, and the light-responsive active material prepared in Example A3 as an additive, the two are blended and then added into a twin-screw extruder for extrusion granulation to obtain a nano-silver antibacterial master batch; wherein the content of the light-responsive active material in the nano-silver antibacterial master batch is 80wt%, and the process parameters of the twin-screw extruder in the preparation process are as follows: the temperature of heating I zone is 235℃, the temperature of heating II zone is 245℃, the temperature of heating III zone is 255℃, the temperature of heating IV zone is 260℃, the temperature of heating V zone is 260℃, the temperature of the die head is 255℃, the rotation speed of the main machine is 36 rpm, and the rotation speed of the feeding machine is 15 rpm.

[0178] The 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on Staphylococcus aureus, Escherichia coli and Candida albicans is 99.9%, 99.9% and 99.9% respectively, the 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on drug-resistant bacteria MRSA is 99.9%, and the 3 min antiviral rate of the nano-silver antibacterial master batch under light conditions on N1H1 virus is 99.9%.

[0179] The 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on Staphylococcus aureus, Escherichia coli and Candida albicans is 99.9%, 99.9% and 99.9% respectively, the 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on drug-resistant bacteria MRSA is 99.9%, and the 3 min antiviral rate of the nano-silver antibacterial master batch under light conditions on N1H1 virus is 99.9%.

[0180] Example B4

[0181] A preparation method of a nano-silver antibacterial master batch, the specific process is as follows:

[0182] A nano-silver antibacterial masterbatch was prepared by blending ECDP (intrinsic viscosity of 0.58 dL / g, melting point of 246°C) as a base material with the light-responsive active material prepared in Example A5 as an additive, and then feeding the blend into a twin-screw extruder for extrusion granulation; the content of the light-responsive active material in the nano-silver antibacterial masterbatch was 75 wt%, and the process parameters of the twin-screw extruder during preparation were as follows: the temperature of heating zone I was 235°C, the temperature of heating zone II was 245°C, the temperature of heating zone III was 255°C, the temperature of heating zone IV was 260°C, the temperature of heating zone V was 260°C, the temperature of the die head was 255°C, the rotation speed of the main machine was 36 rpm, and the rotation speed of the feeding machine was 15 rpm.

[0183] The nano-silver antibacterial masterbatch prepared had 3 min antibacterial rates of 8%, 8%, and 5% against Staphylococcus aureus, Escherichia coli, and Candida albicans respectively under non-illumination conditions, a 3 min antibacterial rate of 8% against drug-resistant bacteria MRSA under non-illumination conditions, and a 3 min antiviral rate of 1% against N1H1 virus under non-illumination conditions.

[0184] The nano-silver antibacterial masterbatch had 3 min antibacterial rates of 99.9%, 99.9%, and 99.9% against Staphylococcus aureus, Escherichia coli, and Candida albicans respectively under illumination conditions, a 3 min antibacterial rate of 99.9% against drug-resistant bacteria MRSA under illumination conditions, and a 3 min antiviral rate of 99.9% against N1H1 virus under illumination conditions.

[0185] Example B5

[0186] A method for preparing a nano-silver antibacterial masterbatch, the specific process being as follows:

[0187] A nano-silver antibacterial masterbatch was prepared by blending ECDP (intrinsic viscosity of 0.58 dL / g, melting point of 246°C) as a base material with the light-responsive active material prepared in Example A5 as an additive, and then feeding the blend into a twin-screw extruder for extrusion granulation; the content of the light-responsive active material in the nano-silver antibacterial masterbatch was 75 wt%, and the process parameters of the twin-screw extruder during preparation were as follows: the temperature of heating zone I was 235°C, the temperature of heating zone II was 245°C, the temperature of heating zone III was 255°C, the temperature of heating zone IV was 260°C, the temperature of heating zone V was 260°C, the temperature of the die head was 255°C, the rotation speed of the main machine was 36 rpm, and the rotation speed of the feeding machine was 15 rpm.

[0188] The nano-silver antibacterial masterbatch prepared had 3 min antibacterial rates of 8%, 8%, and 5% against Staphylococcus aureus, Escherichia coli, and Candida albicans respectively under non-illumination conditions, a 3 min antibacterial rate of 8% against drug-resistant bacteria MRSA under non-illumination conditions, and a 3 min antiviral rate of 1% against N1H1 virus under non-illumination conditions.

[0189] The 3 min antibacterial rates of the nano-silver antibacterial master batch under light conditions on Staphylococcus aureus, Escherichia coli and Candida albicans are 99.9%, 99.9% and 99.9% respectively, the 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on drug-resistant bacteria MRSA is 99.9%, and the 3 min antiviral rate of the nano-silver antibacterial master batch under light conditions on N1H1 virus is 99.9%.

[0190] Example B6

[0191] A preparation method of a nano-silver antibacterial master batch, the specific process is as follows:

[0192] ECDP (intrinsic viscosity is 0.56 dL / g, melting point is 245°C) as a base material, and the light-responsive active material prepared in Example A6 as an additive, and then the two are blended and added into a twin-screw extruder for extrusion granulation to obtain a nano-silver antibacterial master batch; wherein the content of the light-responsive active material in the nano-silver antibacterial master batch is 75 wt%, and the process parameters of the twin-screw extruder in the preparation process are as follows: the temperature of heating I zone is 235°C, the temperature of heating II zone is 245°C, the temperature of heating III zone is 255°C, the temperature of heating IV zone is 260°C, the temperature of heating V zone is 260°C, the temperature of the die head is 255°C, the rotation speed of the main machine is 36 rpm, and the rotation speed of the feeding machine is 15 rpm.

[0193] The 3 min antibacterial rates of the prepared nano-silver antibacterial master batch under non-light conditions on Staphylococcus aureus, Escherichia coli and Candida albicans are 8%, 7% and 8% respectively, the 3 min antibacterial rate of the nano-silver antibacterial master batch under non-light conditions on drug-resistant bacteria MRSA is 8%, and the 3 min antiviral rate of the nano-silver antibacterial master batch under non-light conditions on N1H1 virus is 4%;

[0194] The 3 min antibacterial rates of the nano-silver antibacterial master batch under light conditions on Staphylococcus aureus, Escherichia coli and Candida albicans are 99.91%, 99.92% and 99.91% respectively, the 3 min antibacterial rate of the nano-silver antibacterial master batch under light conditions on drug-resistant bacteria MRSA is 99.93%, and the 3 min antiviral rate of the nano-silver antibacterial master batch under light conditions on N1H1 virus is 99.94%.

Claims

1. A method for preparing a photoresponsive active material, characterized in that, The specific steps are as follows: (a) After mixing PTA, EG, titanium glycol, and sodium acetate, stir for 30-60 min, and then carry out esterification reaction at 245-255℃ and ≤0.1MPa until the output water reaches 90-98% of the theoretical output water; (b) Add EG, SIPM and water-soluble nano silver powder; (c) React at 250-260℃ and 0.1MPa for 15 min; (d) The reaction was carried out at 260-280℃ and ≤0.1MPa until the stirring power of the motor reached 3kW to obtain the photoresponsive active material; The synthesis steps of water-soluble nano-silver powder are as follows: (I) Add SIPM to deionized water and stir at 200-250 rpm at 60-80℃ until clear and transparent; (II) Add water-soluble silver salt solution, keep the temperature and stirring speed constant, and continue stirring for 30-40 minutes; (III) Add ascorbic acid, keep the temperature constant, increase the stirring speed to 400-450 rpm, and react for 2-2.5 h to obtain nano silver hydrosol; (IV) After dialysis purification of the nano-silver hydrosol using a semi-permeable membrane, the dialyzed nano-silver hydrosol was dried to obtain water-soluble nano-silver powder.

2. The method for preparing a photoresponsive active material according to claim 1, characterized in that, The molar ratio of PTA, the first addition of EG, the second addition of EG, SIPM, and water-soluble nano-silver powder is 1:2.55-4.2:1.5-3:1-1.2:1-1.

1.

3. The method for preparing a photoresponsive active material according to claim 1, characterized in that, The amount of titanium glycol added is 6-10 ppm of the total mass of the reaction raw materials, and the amount of sodium acetate added is 1-1.5 wt% of the total mass of the reaction raw materials.

4. The method for preparing a photoresponsive active material according to claim 1, characterized in that, The molar ratio of ascorbic acid to water-soluble silver salt is 2-1.8:1, and the molar ratio of SIPM to water-soluble silver salt is 6-8:

1.

5. A photoresponsive active material, characterized in that, The photoresponsive active material was prepared using the preparation method described in any one of claims 1-4; the photoresponsive active material was dispersed in a layered solution of water and n-hexane, and the photoresponsive active material was uniformly dispersed only in the aqueous layer; the zeta potential of the aqueous solution of the photoresponsive active material with a concentration of 20 mg / L, a temperature of 25°C and a pH of 8 was -43.5 to -44.5 mV; the initial thermal decomposition temperature of the photoresponsive active material was 352-355°C.

6. A nano-silver antibacterial masterbatch, characterized in that, The substrate is ECDP, and the additive is a photoresponsive active material as described in claim 5.

7. The nano-silver antibacterial masterbatch according to claim 6, characterized in that, ECDP has an intrinsic viscosity of 0.5-0.6 dL / g and a melting point of 240-248℃. The content of photoresponsive active materials in the nano-silver antibacterial masterbatch is 70-80 wt%; The nano-silver antibacterial masterbatch showed an antibacterial rate of no more than 10% against Staphylococcus aureus, Escherichia coli, and Candida albicans under light-free conditions, an antibacterial rate of no more than 10% against drug-resistant MRSA under light-free conditions, and an antiviral rate of no more than 5% against N1H1 virus under light-free conditions. The nano-silver antibacterial masterbatch showed an antibacterial rate of over 99.9% against Staphylococcus aureus, Escherichia coli, and Candida albicans under light conditions, an antibacterial rate of over 99.9% against drug-resistant MRSA under light conditions, and an antiviral rate of over 99% against N1H1 virus under light conditions.

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