Preparation method of photocatalytic antibacterial plant fiber

Abstract

The application relates to a preparation method of photocatalytic antibacterial plant fibers. The method comprises the following steps: In2S3 material preparation, PSMA copolymer preparation, thioacetamide preparation, antibacterial performance photocatalyst preparation and photocatalytic antibacterial plant fiber preparation. The photocatalytic antibacterial plant fibers are prepared by creatively combining a heating method, a rectification method, a mixing method, a drying method and a stirring method, and have the advantages of simple preparation process, excellent antibacterial performance, environmental friendliness and the like, and can be applied to multiple fields such as textile and garment, home decoration, medical treatment and health care.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of photocatalytic antibacterial plant fiber and belongs to the technical field of new materials. BACKGROUND

[0002] Bacteria are ubiquitous in every corner of our daily life, and can be said to be everywhere, which can be transmitted through contact, respiratory tract, digestive tract, blood, etc. Bacterial invasion into the human body can cause various diseases. Staphylococcus aureus is a common pathogenic bacterium causing food poisoning, and is the third largest microbial pathogenic bacterium, which has certain resistance to high temperature and can survive in harsh environments. The synthesized photocatalytic antibacterial plant fiber is a promising biological application material, and meanwhile, the crystal type of titanium dioxide has a great influence on the antibacterial activity, but the preparation of the functionalized antibacterial nanocomposite material is particularly complex, and the preparation process has certain harm to the environment. TiO2 has high antibacterial activity under ultraviolet light irradiation, and in combination with the unique antibacterial and bacteriostatic properties of bamboo fiber, the growth of various bacteria can be effectively inhibited, so the preparation of the photocatalytic antibacterial plant fiber is particularly important. SUMMARY

[0003] In view of the above problems, the application provides an environmentally friendly and economically feasible preparation method of photocatalytic antibacterial plant fiber.

[0004] The application provides a preparation method of photocatalytic antibacterial plant fiber, which comprises the following steps: In2S3 material preparation, PSMA copolymer preparation, thioacetamide (TAA) preparation, antibacterial performance photocatalyst preparation and photocatalytic antibacterial plant fiber preparation.

[0005] Preferably, step (1) In2S3 material preparation

[0006] A certain amount of anhydrous ethanol solution and a certain amount of sodium sulfide solution are mixed and stirred until a light yellow sol appears, dilute nitric acid is added dropwise, and then the mixture is transferred to a high-pressure kettle and placed in an oven for hydrothermal reaction at high temperature for a period of time, and then cooled to room temperature, centrifuged with deionized water and anhydrous ethanol solution respectively, and dried in a vacuum oven to obtain the In2S3 material;

[0007] Step (2) PSMA copolymer preparation

[0008] The T-MMA (methyl methacrylate) solution and TiO2-St are added to a three-necked flask in a certain proportion, the In2S3 material of step (1) is added at the same time, and the mixture is placed in a glass mold, the mold is placed in a blast oven, and the mixture is completely polymerized, then the device is taken out, cooled to room temperature, and demolded to obtain the PSMA copolymer.

[0009] Step (3) Preparation of Thioacetamide (TAA)

[0010] The acrylamide and PSMA copolymer of step (2) were mixed in a round bottom flask, benzene was added as a solvent, and after boiling on a water bath, all the materials became semi-liquid, the semi-liquid was discharged, and after cooling, thioacetamide (TAA) was obtained.

[0011] Step (4) Preparation of antibacterial performance photocatalyst

[0012] The thioacetamide (TAA) of step (3) was dissolved in anhydrous ethanol solution, deionized water was added, and it was mixed well, stirred vigorously, and the pH value was adjusted with ammonia water, and then the suspension was transferred to a high-pressure reaction kettle, heated at high temperature for a period of time, and cooled to room temperature. The generated product was collected by centrifugation, and the product was washed with deionized water and anhydrous ethanol solution several times, and finally the centrifugally collected product was placed in a drying oven for a period of time to obtain a photocatalyst with antibacterial performance.

[0013] Step (5) Preparation of photocatalytic antibacterial plant fiber

[0014] The bamboo tube was split into bamboo pieces of a certain width by mechanical means for standby, and a roller mill was used to roll the bamboo in the growth direction, and then soaked in a degumming softener. After soaking for a period of time, the bamboo pieces were taken out and rolled out along the growth direction of the bamboo using a roller mill, and then steamed. The rolled-out bamboo pieces were heated together with the degumming softener while applying pressure to further separate the fibers from other tissues. The steamed bamboo pieces were washed with water, carded into coarse fibers, and then steamed again. The antibacterial photocatalyst of step (4) was added, heated at high temperature, taken out, and dried to obtain photocatalytic antibacterial plant fiber.

[0015] As preferred, step (1) Preparation of In2S3 material

[0016] 40-50 mL of 0.2-0.5 mol / L anhydrous ethanol solution and 40-50 mL of 0.5-0.8 mol / L sodium sulfide solution were taken, the two solutions were mixed and stirred until a uniform light yellow sol was obtained, 10-20% dilute nitric acid was added to adjust the pH of the solution to 3-7, and then transferred to a 100-200 mL autoclave and placed in an oven at 180-200°C for 18-22h of hydrothermal reaction. After the hydrothermal reaction was completed, the solution was cooled to room temperature, and then centrifuged with deionized water and anhydrous ethanol solution for 3-6 times, and then placed in a vacuum oven at 80-95°C for drying for 14-18h to obtain the In2S3 material.

[0017] The application has the advantages that the band structure can be optimized by the hydrothermal synthesis, the effective separation of the electron-hole pairs is promoted, a large number of active oxygen species are generated in water or on the surface, the active oxygen species have strong oxidizing properties, the cell walls and membrane structures of bacteria can be destroyed, and the purposes of bacteriostasis and sterilization are achieved.

[0018] As preferred, the preparation of the PSMA copolymer in step (2)

[0019] The T-MMA (methyl methacrylate) solution and 5-10 w% TiO2-St are added into a three-necked flask in a ratio of 1-5:3-8, 10-20 g of the In2S3 material in step (1) is added, and the flask is placed in a glass mold, the mold is placed in a blast oven at 100-200 DEG C, and the mold is completely polymerized, after the polymerization is completed, the device is taken out, and after being cooled to room temperature of 20-30 DEG C, the PSMA copolymer is obtained by demolding.

[0020] The application has the advantages that the PSMA copolymer not only wraps and fixes the In2S3 and TiO2 particles, improves the mechanical strength of the whole, but also enhances the binding force between the particles and the matrix through the covalent bond, so that the material is more durable in actual application, is not easy to wear or fall off, and the service life is prolonged.

[0021] As preferred, the preparation of the thioacetamide (TAA) in step (3)

[0022] 59-79 g of acetamide and 44-54 g of the PSMA copolymer in step (2) are mixed in a 2.5-6 L round-bottom flask, 1-4 L of benzene is added as a solvent, after being boiled on a water bath for 20-50 minutes, all the substances become a semi-liquid state, the semi-liquid is guided out, the semi-liquid is concentrated to 300-400 mL, and after being cooled, the thioacetamide (TAA) is obtained.

[0023] The application has the advantages that benzene is used as a solvent, has good solubility, helps the uniform dissolution of the thioacetamide (TAA), is easy to become a semi-liquid, and is easy to form the thioacetamide (TAA).

[0024] As preferred, the preparation of the antibacterial performance photocatalyst in step (4)

[0025] Dissolve 5-10 mmol of thioacetamide (TAA) of step (3) in 10-20 mL of anhydrous ethanol solution, add 40-60 mL of deionized water, mix well, stir vigorously, and adjust the pH to 10-20 with ammonia water, continue stirring for 2-5 h, transfer the obtained suspension to a 100-200 mL Telfon high-pressure reactor, heat to 200-300 DEG C for 15-20 h, cool to room temperature, collect the generated product by centrifugation, and wash the obtained product with deionized water and anhydrous ethanol solution for 3-5 times, and finally dry the centrifugally collected product in a drying oven at 80-100 DEG C for 12-15 h to obtain a photocatalyst with antibacterial properties.

[0026] The present application has the advantages that, through careful control of the synthesis conditions, the prepared photocatalyst can effectively absorb and utilize light energy, activate the surface electron-hole pairs, produce active species with strong oxidizing properties, and destroy the cell wall and membrane structure of bacteria, thereby exhibiting excellent antibacterial effect.

[0027] As preferred, step (5) preparation of photocatalytic antibacterial plant fibers

[0028] Mechanically split 10-30 g of bamboo tubes into 3-5 cm wide bamboo pieces for use, use a roller mill to initially roll the bamboo in the growth direction, then soak the bamboo pieces in a degumming softener, the degumming softener and water are mixed at a ratio of 1-5:3-8, after soaking for 4-6 hours, take out the bamboo pieces and use a roller mill to roll and expand the bamboo in the growth direction, then cook the rolled and expanded bamboo pieces together with the degumming softener to 150-200 DEG C while applying a pressure of 0.2-0.8 MPa to further separate the fibers from other tissues, cook for 5-10 h to fully remove sugar, fat and gum, wash out the cooked bamboo pieces, card them into coarse fibers, and then cook for 3-6 h, add 5-10 mL of the antibacterial photocatalyst of step (4), heat to 130-200 DEG C, take out and dry to obtain photocatalytic antibacterial plant fibers.

[0029] The present application has the advantages that, using natural bamboo as raw material, bamboo has a short growth cycle and strong regenerative ability, and is a sustainable biomass resource, greatly reducing the pressure on the environment compared to traditional chemical fibers, and by directly incorporating the antibacterial photocatalyst into the plant fibers, not only the antibacterial ability of the fibers is enhanced, but also the antibacterial effect can be continuously exerted under light conditions, effectively inhibiting bacterial growth.

[0030] In summary, the present application has the following advantages:

[0031] 1. The application has the advantages that the band structure can be optimized by hydrothermal synthesis, promoting the effective separation of electron-hole pairs, thereby generating a large number of active oxygen species in water or on the surface, which have strong oxidizing properties and can destroy the cell wall and membrane structure of bacteria, thereby achieving the purpose of efficiently killing bacteria.

[0032] 2. The application has the advantages that the formation of the PSMA copolymer not only encapsulates and fixes the In2S3 and TiO2 particles, improves the overall mechanical strength, and enhances the bonding force between the particles and the matrix through covalent bonds, so that the material is more durable in actual application and is not easy to wear or fall off, prolonging the service life.

[0033] 3. The application has the advantages that benzene is used as a solvent, which has good solubility and helps uniform dissolution of thioacetamide (TAA), easy formation of thioacetamide (TAA), and easy formation of thioacetamide (TAA).

[0034] 4. The application has the advantages that the prepared photocatalyst can effectively absorb and utilize light energy, activate the surface electron-hole pairs, generate active species with strong oxidizing properties, and destroy the cell wall and membrane structure of bacteria, thereby exhibiting excellent antibacterial effect.

[0035] 5. The application has the advantages that natural bamboo is used as a raw material, bamboo has a short growth cycle and strong regenerative ability, and is a sustainable biomass resource, which greatly reduces the pressure on the environment compared to traditional chemical fibers, and the photocatalyst with antibacterial performance is directly integrated into the plant fiber, not only enhancing the antibacterial ability of the fiber itself, but also continuously exerting antibacterial effect under light conditions, effectively inhibiting bacterial growth. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 A flowchart of a preparation method of a photocatalytic antibacterial plant fiber. DETAILED DESCRIPTION

[0037] The following examples are used to illustrate the present application, but are not used to limit the scope of the present application. Modifications or replacements of the methods, steps or conditions of the present application without departing from the spirit and essence of the present application all belong to the scope of the present application.

[0038] If not specifically indicated, the technical means used in the examples is the conventional means known to those skilled in the art. In addition, all the component raw materials used in the examples are known commercially available products. Example 1

[0039] Step (1) Preparation of In2S3 material

[0040] Take 40 mL of 0.2 mol / L anhydrous ethanol solution and 40 mL of 0.5 mol / L sodium sulfide solution, mix the two solutions and stir until a uniform light yellow sol is formed, add 10% dilute nitric acid to adjust the pH of the solution to 3, and transfer to a 100 mL autoclave, place in an oven at 180°C for 18 h, cool to room temperature after the hydrothermal reaction is completed, centrifuge with deionized water and anhydrous ethanol solution for 3 times respectively, and dry in a vacuum oven at 80°C for 14 h to obtain In2S3 material;

[0041] Step (2) Preparation of PSMA copolymer

[0042] Add T-MMA (methyl methacrylate) solution and 5w% TiO2-St to a three-necked flask in a ratio of 1:3, add 10 g of In2S3 material of step (1) at the same time, and place in a glass mold, put the mold into a 100°C air oven to make it completely polymerize, after polymerization is completed, take out the device, cool to room temperature of 20°C, and demold to obtain PSMA copolymer;

[0043] Step (3) Preparation of thioacetamide (TAA)

[0044] Put 59 g of acetamide and 44 g of PSMA copolymer in step (2) into a 2.5 L round-bottom flask, mix, add 1 L of benzene as solvent, boil on a water bath for 20 minutes, and all the substances become semi-fluid state, lead out the semi-fluid, concentrate to 300 mL, cool, and obtain thioacetamide (TAA);

[0045] Step (4) Preparation of antibacterial performance photocatalyst

[0046] Dissolve 5 mmol of thioacetamide (TAA) of step (3) into 10 mL of anhydrous ethanol solution, add 40 mL of deionized water, mix well, stir vigorously, adjust the pH to 10 with ammonia water, continue stirring for 2 h, transfer the obtained suspension to a 100 mL Telfon autoclave, heat to 200°C for 15 h, cool to room temperature, collect the generated product by centrifugation, and wash the obtained product with deionized water and anhydrous ethanol solution for 3 times, finally put the centrifuged product into a drying oven at 80°C for 12 h to obtain a photocatalyst with antibacterial performance;

[0047] Step (5) Preparation of photocatalytic antibacterial plant fiber

[0048] 10g of bamboo tube is mechanically split into 3cm wide bamboo pieces for use, initial rolling is performed along the growth direction of the bamboo using a roller mill, and then soaking is performed. The bamboo pieces are soaked in a degumming softener, and the degumming softener and water are mixed at a ratio of 1:3. After soaking for 4 hours, the bamboo pieces are taken out and rolled out along the growth direction of the bamboo using a roller mill. The rolled-out bamboo pieces are then steamed. The rolled-out bamboo pieces and the degumming softener are heated to 150°C while applying a pressure of 0.2 MPa to further separate the fibers from other tissues. The steaming is performed for 5 hours to sufficiently remove sugar, fat, and gum. The steamed bamboo pieces are washed with water and taken out. The bamboo pieces are carded into coarse fibers, and then steamed for 3 hours. 5 mL of the antibacterial photocatalyst of step (4) is added, and the mixture is heated to 130°C. The mixture is taken out and dried to obtain the photocatalytic antibacterial plant fibers. Example 2

[0049] Step (1) Preparation of In2S3 material

[0050] 43 mL of 0.3 mol / L anhydrous ethanol solution and 43 mL of 0.6 mol / L sodium sulfide solution are mixed and stirred until a uniform light yellow sol is obtained. 15% dilute nitric acid is added dropwise to adjust the pH of the solution to 5. The solution is transferred to a 110 mL autoclave and placed in an oven at 190°C for hydrothermal reaction for 19 hours. After the hydrothermal reaction is completed, the solution is cooled to room temperature and centrifuged with deionized water and anhydrous ethanol solution for 4 times respectively. The solution is then placed in a vacuum oven at 85°C for drying for 15 hours to obtain the In2S3 material.

[0051] Step (2) Preparation of PSMA copolymer

[0052] A T-MMA (methyl methacrylate) solution and 7 w% TiO2-St are added to a three-necked flask in a ratio of 2:4, and 15 g of the In2S3 material of step (1) is added. The mixture is placed in a glass mold, and the mold is placed in a 120°C air oven to complete polymerization. After polymerization is completed, the device is taken out and cooled to room temperature. The PSMA copolymer is obtained by demolding.

[0053] Step (3) Preparation of thioacetamide (TAA)

[0054] 60 g of acetamide and 46 g of the PSMA copolymer of step (2) are mixed in a 3L round-bottom flask, and 2L of benzene is added as a solvent. The mixture is boiled on a water bath for 25 minutes until all the substances become a semi-liquid state. The semi-liquid is discharged and concentrated to 320 mL. After cooling, thioacetamide (TAA) is obtained.

[0055] Step (4) Preparation of antibacterial photocatalyst

[0056] Dissolve 6 mmol of thioacetamide (TAA) of step (3) in 12 mL of anhydrous ethanol solution, add 45 mL of deionized water, mix well, stir vigorously, adjust the pH to 12 with ammonia water, continue stirring for 2.5 h, transfer the resulting suspension to a 110 mL Telfon autoclave, heat to 210°C for 16-20 h, cool to room temperature, collect the product by centrifugation, and wash the product with deionized water and anhydrous ethanol solution for 4 times, and finally dry the centrifugally collected product in a drying oven at 85°C for 13 h to obtain a photocatalyst with antibacterial properties;

[0057] Step (5) Preparation of photocatalytic antibacterial plant fibers

[0058] Split 11 g of bamboo into 4 cm wide bamboo pieces by mechanical means for standby, use a roller mill to roll the bamboo in the growth direction, then soak the bamboo pieces in a degumming softener, the degumming softener and water are mixed at a ratio of 2:4, after soaking for 5 hours, take out the bamboo pieces and use a roller mill to roll and expand the bamboo in the growth direction, then cook the rolled and expanded bamboo pieces together with the degumming softener to 160°C while applying a pressure of 0.3 MPa to further separate the fibers from other tissues, cook for 6 h to fully remove sugar, fat and gum, wash the cooked bamboo pieces with water, card them into coarse fibers, and then cook for 4 h, add 6 mL of antibacterial photocatalyst of step (4), heat to 140°C, take out and dry to obtain photocatalytic antibacterial plant fibers. Example 3

[0059] Step (1) Preparation of In2S3 material

[0060] Take 44 mL of 0.4 mol / L anhydrous ethanol solution and 44 mL of 0.7 mol / L sodium sulfide solution, mix and stir the two solutions until a uniform light yellow sol is obtained, add 16% dilute nitric acid to adjust the pH of the solution to 5.5, and transfer to a 120 mL autoclave, place in an oven at 195°C for 20 h of hydrothermal reaction, cool to room temperature after the hydrothermal reaction is completed, centrifuge with deionized water and anhydrous ethanol solution for 5 times respectively, and dry in a vacuum oven at 87°C for 16 h to obtain In2S3 material;

[0061] Step (2) Preparation of PSMA copolymer

[0062] T-MMA (methyl methacrylate) solution and 8w% TiO2-St were added into a three-necked flask in a ratio of 3:5, 16g of In2S3 material from step (1) was added, and the flask was placed in a glass mold, which was put into a blast oven at 130°C to make it fully polymerize. After polymerization was completed, the device was removed, cooled to room temperature at 25°C, and then demolded to obtain a PSMA copolymer;

[0063] Step (3) Preparation of thioacetamide (TAA)

[0064] 70g of acetamide and 50g of PSMA copolymer from step (2) were mixed in a 3.5L round-bottom flask, 2.5L of benzene was added as a solvent, and the mixture was boiled on a water bath for 30 minutes. After that, all the materials became semi-liquid, and the semi-liquid was discharged and concentrated to 350mL. After cooling, thioacetamide (TAA) was obtained.

[0065] Step (4) Preparation of antibacterial photocatalyst

[0066] 7mmol of thioacetamide (TAA) from step (3) was dissolved in 13mL of anhydrous ethanol solution, 50mL of deionized water was added, and the mixture was stirred vigorously and adjusted to pH 14 with ammonia water. The resulting suspension was then transferred to a 120mL Telfon high-pressure reactor and heated to 220°C for 18h. After cooling to room temperature, the generated product was collected by centrifugation, and the resulting product was washed with deionized water and anhydrous ethanol solution for 5 times. Finally, the centrifugally collected product was placed in a drying oven at 90°C for 14h to obtain an antibacterial photocatalyst.

[0067] Step (5) Preparation of photocatalytic antibacterial plant fiber

[0068] A 12g bamboo tube was mechanically split into 5cm wide bamboo pieces for use. A roller mill was used to roll the bamboo in the growth direction, and then the bamboo was soaked in a degumming softener with a concentration ratio of 3:5. After soaking for 6 hours, the bamboo was taken out and rolled out using a roller mill in the growth direction. The rolled bamboo was then steamed together with the degumming softener, heated to 170°C, and subjected to a pressure of 0.4MPa to further separate the fibers from other tissues. The steamed bamboo was then washed with water, combed into coarse fibers, and steamed again for 5h. 6.5mL of the antibacterial photocatalyst from step (4) was added, heated to 150°C, and then taken out and dried to obtain photocatalytic antibacterial plant fiber. Example 4

[0069] Step (1) Preparation of In2S3 material

[0070] Take 50 mL of 0.5 mol / L anhydrous ethanol solution and 50 mL of 0.8 mol / L sodium sulfide solution, mix the two solutions and stir until a uniform light yellow sol is formed, add 20% dilute nitric acid to adjust the pH of the solution to 7, and transfer to a 150 mL autoclave, place in the oven at 200°C for 21 h, cool to room temperature after the hydrothermal reaction is completed, centrifuge with deionized water and anhydrous ethanol solution for 6 times respectively, and dry in a vacuum oven at 90°C for 17 h to obtain In2S3 material;

[0071] Step (2) Preparation of PSMA copolymer

[0072] Add T-MMA (methyl methacrylate) solution and 9w% TiO2-St to a three-necked flask in a ratio of 4:6, add 18 g of In2S3 material of step (1) at the same time, and place it in a glass mold, put the mold into a 160°C air oven to make it completely polymerize, after polymerization, take out the device, cool to room temperature, and demold to obtain the PSMA copolymer;

[0073] Step (3) Preparation of thioacetamide (TAA)

[0074] Put 76 g of acetamide and 54 g of PSMA copolymer in step (2) into a 5 L round-bottom flask, add 3.5 L of benzene as solvent, boil on a water bath for 40 minutes, and all the materials become semi-liquid state, then lead out the semi-liquid, concentrate to 370 mL, cool, and obtain thioacetamide (TAA);

[0075] Step (4) Preparation of antibacterial performance photocatalyst

[0076] Dissolve 8 mmol of thioacetamide (TAA) of step (3) in 15 mL of anhydrous ethanol solution, add 60 mL of deionized water, mix well, stir vigorously, and adjust the pH to 17 with ammonia water, continue stirring for 4 h, transfer the obtained suspension to a 150 mL Telfon autoclave, heat to 250°C for 19 h, cool to room temperature, collect the generated product by centrifugation, and wash the obtained product with deionized water and anhydrous ethanol solution for 5 times, finally put the centrifuged product into a drying oven at 100°C for 15 h to obtain a photocatalyst with antibacterial performance;

[0077] Step (5) Preparation of photocatalytic antibacterial plant fiber

[0078] The 13 g of bamboo tube is mechanically split into 6 cm wide bamboo pieces for standby, and a roller mill is used to roll the bamboo in the growth direction, and then soaked in a degumming softener, and the degumming softener and water are mixed at a ratio of 4:6, and after soaking for 7 hours, the bamboo pieces are taken out and rolled out along the growth direction of the bamboo using a roller mill, and then steamed, and the rolled out bamboo pieces are heated to 180℃ together with the degumming softener, and at the same time, 0.5 MPa pressure is applied to further separate the fibers from other tissues, and the steaming is carried out for 8 h to fully remove sugar, fat and glue, and the steamed bamboo pieces are washed and taken out, and then combed into coarse fibers, and then steamed for 6 h, and 7 mL of step (4) antibacterial photocatalyst is added, and heated to 200℃, and taken out and dried to obtain a photocatalytic antibacterial plant fiber. Comparative Example 1

[0079] Step (1) Preparation of In2S3 material

[0080] 60 mL of 0.6 mol / L anhydrous ethanol solution and 60 mL of 0.9 mol / L sodium sulfide solution were taken, and the two solutions were mixed and stirred until a uniform light yellow sol was obtained. 30% dilute nitric acid was added to adjust the pH of the solution to 8, and then transferred to a 160 mL autoclave and placed in an oven at 210℃ for hydrothermal reaction for 22 h. After the hydrothermal reaction was completed, it was cooled to room temperature, and then centrifuged with deionized water and anhydrous ethanol solution for 7 times respectively, and then placed in a 95℃ vacuum oven for drying for 18 h to obtain the In2S3 material.

[0081] Step (2) Preparation of PSMA copolymer

[0082] A T-MMA (methyl methacrylate) solution and 10 w% TiO2-St were added to a three-necked flask at a ratio of 5:7, and 19 g of In2S3 material of step (1) was added, and then placed in a glass mold, and the mold was placed in a 170℃ air oven to complete polymerization. After polymerization was completed, the device was removed, cooled to room temperature, and then demolded to obtain the PSMA copolymer.

[0083] Step (3) Preparation of thioacetamide (TAA)

[0084] 80 g of acetamide and 55 g of PSMA copolymer in step (2) were placed in a 5 L round-bottom flask and mixed, and then 4 L of benzene was added as a solvent. After boiling for 45 minutes on a water bath, all the materials became semi-liquid. The semi-liquid was discharged and concentrated to 380 mL. After cooling, thioacetamide (TAA) was obtained.

[0085] Step (4) Preparation of antibacterial photocatalyst

[0086] Dissolve 9 mmol of thioacetamide (TAA) of step (3) in 20 mL of anhydrous ethanol solution, add 65 mL of deionized water, mix well, stir vigorously, and adjust the pH to 20 with ammonia water, continue stirring for 5 h, transfer the obtained suspension to a 200 mL Telfon autoclave, heat to 300°C for 20 h, cool to room temperature, collect the generated product by centrifugation, and wash the obtained product with deionized water and anhydrous ethanol solution for 6 times, and finally put the centrifugally collected product into a drying oven at 110°C for 16 h to obtain a photocatalyst with antibacterial properties. Comparative Example 2

[0087] Step (1) Preparation of PSMA copolymer

[0088] Add a T-MMA (methyl methacrylate) solution and 11 w% TiO2-St to a three-necked flask in a ratio of 6:8, add 20 g of In2S3 material at the same time, and place it in a glass mold, put the mold into a 180°C air oven, and make it fully polymerize, after polymerization is completed, take out the device, cool to room temperature of 30°C, and demold to obtain a PSMA copolymer;

[0089] Step (2) Preparation of thioacetamide (TAA)

[0090] Put 90 g of acetamide and 60 g of PSMA copolymer together in a 6 L round-bottom flask, add 5 L of benzene as a solvent, boil on a water bath for 50 minutes, and all the substances become semi-fluid, lead out the semi-fluid, concentrate to 390 mL, cool, and obtain thioacetamide (TAA);

[0091] Step (3) Preparation of antibacterial photocatalyst

[0092] Dissolve 10 mmol of thioacetamide (TAA) in 25 mL of anhydrous ethanol solution, add 70 mL of deionized water, mix well, stir vigorously, and adjust the pH to 21 with ammonia water, continue stirring for 6 h, transfer the obtained suspension to a 210 mL Telfon autoclave, heat to 310°C for 25 h, cool to room temperature, collect the generated product by centrifugation, and wash the obtained product with deionized water and anhydrous ethanol solution for 7 times, and finally put the centrifugally collected product into a drying oven at 100°C for 15 h to obtain a photocatalyst with antibacterial properties;

[0093] Step (4) Preparation of photocatalytic antibacterial plant fiber

[0094] The 15 g bamboo tube is mechanically split into 7 cm wide bamboo pieces for standby, and a roller mill is used to roll the bamboo in the growth direction. Then the bamboo pieces are soaked in a degumming softener, and the degumming softener and water are mixed at a ratio of 5:7. After soaking for 8 hours, the bamboo pieces are taken out and rolled out using a roller mill along the growth direction of the bamboo. Then the rolled-out bamboo pieces are steamed together with the degumming softener, heated to 190°C, and a pressure of 0.6 MPa is applied to further separate the fibers from other tissues. The steaming is carried out for 9 hours to fully remove sugar, fat and gum. The steamed bamboo pieces are washed and taken out, and the coarse fibers are carded and steamed again for 7 hours. Then 8 mL of the antibacterial photocatalyst of step (3) is added, heated to 210°C, taken out, and dried to obtain the photocatalytic antibacterial plant fiber.

[0095] The photocatalytic antibacterial plant fibers obtained in Examples 1 to 4 and Comparative Product 1 and 2 are tested, and the specific testing method is as follows:

[0096] Photocatalytic activity test method

[0097] The photocatalytic activity test method mainly evaluates the light absorption, separation of photo-generated electrons and holes, and charge injection efficiency. The optical performance of the photocatalytic antibacterial plant fiber is tested by visible diffuse reflectance spectroscopy, and the absorption ability of the photocatalytic antibacterial plant fiber in the visible light range is analyzed. Stronger light absorption ability usually means that the photocatalytic antibacterial plant fiber can capture more photons, thereby generating more excited state electron-hole pairs in the photocatalytic process, indicating that the photocatalytic activity is stronger.

[0098] Inhibition zone method

[0099] TiO2 in the photocatalytic antibacterial plant fiber is used as a photocatalytic antibacterial element. Under the action of ultraviolet light, reactive oxygen species are generated to directly attack microbial cells, causing cell protein variation and lipid decomposition to kill bacteria. The inhibition zone method is used to test the antibacterial performance of Staphylococcus aureus. The larger the inhibition zone diameter, the stronger the inhibition of the antibacterial drug on the test bacteria under the test conditions, indicating better antibacterial effect.

[0100] Halo test method

[0101] The bamboo fiber in the photocatalytic antibacterial plant fiber has good antibacterial, anti-mite and anti-mold properties, and can inhibit the growth of various bacteria, fungi and microorganisms. Different amounts of crosslinking agent are added to test the antibacterial performance of the photocatalytic antibacterial plant fiber. In this test, Escherichia coli is used as the experimental strain.

[0102]

[0103] As can be seen from Table 1, Example 1 is the best, and Comparative Example 1 is the worst. In the photocatalytic activity test method, the light absorbance of Example 1 is the strongest, showing the highest photocatalytic activity, indicating that it can more effectively convert and degrade the target substance in the photocatalysis process, because the high reactivity, good light absorption capacity, and more efficient electron-hole pair separation efficiency of the photocatalytic antibacterial plant fiber, the higher photocatalytic activity indicates that the photocatalytic antibacterial plant fiber has better stability under light, can continuously drive the catalytic reaction without easy deactivation or decomposition, indicating that the stronger the photocatalytic activity.

[0104]

[0105] As can be seen from Table 2, Example 1 is the best, and Comparative Example 2 is the worst. In the inhibition zone method, TiO2 in the photocatalytic antibacterial plant fiber as a high-efficiency photocatalyst can activate to produce highly reactive free radicals when subjected to ultraviolet light, which has a strong destructive ability to microbial cells, can attack and destroy the cell wall, membrane structure and internal biomolecules of bacteria, thereby efficiently killing bacteria. The inhibition zone diameter of Example 1 is the largest, indicating that the photocatalytic antibacterial plant fiber produces the most active oxygen species under light, and has the strongest inhibition effect on Staphylococcus aureus, so the antibacterial effect is the best.

[0106]

[0107] As can be seen from Table 3, Example 1 is the best, and Comparative Example 2 is the worst. In the halo test method test, the inhibition zone diameter of the photocatalytic antibacterial plant fiber of Example 1 is the largest, indicating that the density of the plant fiber is smaller, the voids of the fiber are more, and the antibacterial agent has good permeability to the photocatalytic antibacterial plant fiber, indicating that the photocatalytic antibacterial plant fiber has good antibacterial performance, and the antibacterial performance of the photocatalytic antibacterial plant fiber is excellent.

[0108] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, as long as the modifications are within the scope of the claims of the present application, and are protected by the Patent Law.

Claims

1. A method for preparing a photocatalytic antibacterial plant fiber, characterized by, The preparation of In2S3 material, the preparation of PSMA copolymer, the preparation of thioacetamide, the preparation of antibacterial performance photocatalyst, the preparation of photocatalytic antibacterial plant fiber; Step (1) preparation of In2S3 material Take a certain amount of anhydrous ethanol solution and a certain amount of sodium sulfide solution, mix the two solutions and stir until a light yellow sol appears, add dilute nitric acid dropwise, and transfer to an autoclave, place in an oven at high temperature, and hydrothermal reaction for a period of time, then cool to room temperature, centrifuge with deionized water and anhydrous ethanol solution respectively, place in a vacuum oven to dry, and obtain In2S3 material; Step (2) preparation of PSMA copolymer Add T-MMA solution and TiO2-St to a three-necked flask in a certain proportion, add In2S3 material of step (1) at the same time, and place in a glass mold. Put the mold into a forced air oven to make it completely polymerize. After polymerization is complete, remove the device, cool to room temperature, and demold to obtain PSMA copolymer. Step (3) preparation of thioacetamide Put acetamide and PSMA copolymer of step (2) in a round-bottom flask, mix, add benzene as solvent, boil on a water bath, and all substances become semi-liquid state. Lead out the semi-liquid, concentrate, cool, and obtain thioacetamide. Step (4) preparation of antibacterial performance photocatalyst Dissolve thioacetamide of step (3) in anhydrous ethanol solution, add deionized water, mix thoroughly, stir, adjust pH value with ammonia water, continue stirring, transfer the obtained suspension to a high-pressure reaction kettle, heat at high temperature for a period of time, cool to room temperature, collect the generated product by centrifugation, wash the obtained product with deionized water and anhydrous ethanol solution for several times, and finally dry the centrifugally collected product in a drying box for a period of time to obtain a photocatalyst with antibacterial performance. Step (5) preparation of photocatalytic antibacterial plant fiber Split the bamboo tube into bamboo pieces of a certain width by mechanical means for standby use. Use a roller mill to roll the bamboo pieces in the growth direction of the bamboo. Soak the bamboo pieces in a degumming softener. After soaking for a period of time, take out the bamboo pieces and roll them out in the growth direction of the bamboo using a roller mill. Steam the rolled-out bamboo pieces together with the degumming softener while applying pressure to further separate the fibers from other tissues. Steam the bamboo pieces again, add the antibacterial performance photocatalyst of step (4), heat at high temperature, take out, and air dry to obtain photocatalytic antibacterial plant fiber.

2. The preparation method of photocatalytic antibacterial plant fiber according to claim 1, characterized in that: Step (1) preparation of In2S3 material ​ Take 40-50 mL of 0.2-0.5 mol / L anhydrous ethanol solution and 40-50 mL of 0.5-0.8 mol / L sodium sulfide solution, mix the two solutions and stir until a uniform light yellow sol is formed, add 10-20% dilute nitric acid to adjust the pH of the solution to 3-7, and transfer to a 100-200 mL autoclave, place in an oven at 180-200°C for 18-22 hours, cool to room temperature, centrifuge 3-6 times with deionized water and anhydrous ethanol solution, and dry in a vacuum oven at 80-95°C for 14-18 hours to obtain In2S3 material.

3. The preparation method of photocatalytic antibacterial plant fiber according to claim 2, characterized in that: Step (2) Preparation of PSMA copolymer The T-MMA solution and 5-10 w% TiO2-St are added to a three-necked flask in a ratio of 1-5:3-8, 10-20 g of In2S3 material from step (1) is added, and the mold is placed in a 100-200°C air oven to allow complete polymerization. After polymerization is complete, remove the device, cool to room temperature of 20-30°C, and demold to obtain the PSMA copolymer.

4. The preparation method of photocatalytic antibacterial plant fiber according to claim 3, characterized in that: Step (3) Preparation of thioacetamide Place 59-79 g of acetamide and 44-54 g of PSMA copolymer from step (2) in a 2.5-6 L round-bottom flask, mix, and add 1-4 L of benzene as a solvent. Boil on a water bath for 20-50 minutes until all the materials become semi-liquid. Remove the semi-liquid and concentrate it to 300-400 mL. After cooling, thioacetamide is obtained.

5. The preparation method of photocatalytic antibacterial plant fiber according to claim 4, characterized in that: Step (4) Preparation of antibacterial performance photocatalyst Dissolve 5-10 mmol of thioacetamide from step (3) in 10-20 mL of anhydrous ethanol solution, add 40-60 mL of deionized water, mix well, stir vigorously, and adjust the pH to 10-20 with ammonia water. Continue stirring for 2-5 hours. Transfer the obtained suspension to a 100-200 mL Telfon autoclave and heat to 200-300°C for 15-20 hours. Cool to room temperature, collect the generated product by centrifugation, and wash the obtained product with deionized water and anhydrous ethanol solution for 3-5 times. Finally, place the centrifugally collected product in a drying oven at 80-100°C for 12-15 hours to obtain a photocatalyst with antibacterial performance.

6. The preparation method of photocatalytic antibacterial plant fiber according to claim 5, characterized in that: Step (5) Preparation of photocatalytic antibacterial plant fiber The 10-30g bamboo tube is split into 3-5cm wide bamboo pieces by mechanical method for standby, the initial rolling is carried out along the growth direction of the bamboo by using a roller mill, then the bamboo pieces are soaked in a degumming softener, the degumming softener and water are mixed at a ratio of 1-5:3-8, after soaking for 4-6 hours, the bamboo pieces are taken out and rolled and spread along the growth direction of the bamboo by using a roller mill, then the bamboo pieces are cooked, the rolled and spread bamboo pieces are heated to 150-200℃ together with the degumming softener, and at the same time, 0.2-0.8MPa pressure is applied to further separate the fibers from other tissues, the cooking is carried out for 5-10h to sufficiently remove the sugar, fat and gum, the cooked bamboo pieces are washed and taken out, carded into coarse fibers, then cooked again for 3-6h, 5-10mL of the antibacterial photocatalyst in step (4) is added, heated to 130-200℃, taken out and dried to obtain the photocatalytic antibacterial plant fibers.

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