Bio-based antibacterial monofilament preparation method and bio-based antibacterial monofilament

Abstract

The invention discloses a bio-based antibacterial monofilament preparation method and a bio-based antibacterial monofilament. Silver ion loaded polyporphyrin is prepared, and the mass percent of silver ions is 8-12%; preparing silver ion loaded polyporphyrin modified bio-based polyurethane, wherein the mass percentage of the silver ion loaded polyporphyrin is 10%-20%; and adding the silver ion-loaded polyporphyrin modified bio-based polyurethane and bio-based polyester into a single screw extruder for extrusion spinning to obtain the bio-based antibacterial monofilament, and the bio-based antibacterial monofilament is of a skin-core structure. According to the technical scheme provided by the embodiment of the invention, the silver ions are loaded through the polyporphyrin, and the polyporphyrin is co-constructed by an organic connector through a covalent bond and has excellent stability, high surface area and large voids, so that when the silver ions are coordinated to the polyporphyrin carrier, the silver ions have relatively good dispersity and are not easy to fall off, and the silver ions are loaded on the polyporphyrin carrier. The antibacterial effect can be maintained for a long time, and the antibacterial time is prolonged.

Description

Technical Field

[0001] The present invention generally relates to the field of monofilaments, and in particular to a method for preparing a bio-based antibacterial monofilament and a bio-based antibacterial monofilament. Background Art

[0002] Because a lot of chemical additives are added in the process of preparing polyester with PET (polyethylene terephthalate) as raw material, and PET has poor water and sweat absorption, it is easy to accumulate sweat, produce bacteria and odor. Therefore, metal ions are generally added to PET materials for sterilization. Metal ions such as manganese, zinc, silver, mercury, copper, etc. have strong bactericidal ability, among which silver, copper, and zinc are used more. Among these three metal ions, the antibacterial ability of silver ions is much stronger than that of zinc and copper, and silver ions have excellent properties such as broad-spectrum antibacterial, good heat resistance, good dispersibility, and low drug resistance.

[0003] However, silver ions added to PET will fall off after long-term use, resulting in weakened antibacterial ability and shortened antibacterial duration. On the other hand, if silver ions precipitate too quickly and the concentration is too high, it will have a certain impact on the human body. Summary of the invention

[0004] In view of the above-mentioned defects or deficiencies in the prior art, it is desirable to provide a method for preparing a bio-based antibacterial monofilament and a bio-based antibacterial monofilament.

[0005] In a first aspect, a method for preparing a bio-based antibacterial monofilament is provided, the method comprising: Preparation of polyporphyrin loaded with silver ions: providing polyporphyrin, dissolving silver acetate and the polyporphyrin under certain conditions, obtaining unreduced polyporphyrin loaded with silver ions, reducing the unreduced polyporphyrin loaded with silver ions with hydrogen, and obtaining polyporphyrin loaded with silver ions, wherein the mass percentage of silver ions is 8-12%; Preparation of silver ion-loaded polyporphyrin-modified bio-based polyurethane: grinding the silver ion-loaded polyporphyrin into powder, adding the powder and the bio-based polyurethane into a twin-screw extruder according to a certain mass ratio for extrusion granulation, wherein the mass percentage of the silver ion-loaded polyporphyrin is 10%-20%, and obtaining silver ion-loaded polyporphyrin-modified bio-based polyurethane particles; Preparation of bio-based antibacterial monofilament: adding the bio-based polyporphyrin-modified bio-based polyurethane loaded with silver ions and bio-based polyester into a single-screw extruder for extrusion spinning to obtain the bio-based antibacterial monofilament, wherein the bio-based antibacterial monofilament is a skin-core structure, the bio-based polyporphyrin-modified bio-based polyurethane loaded with silver ions is the skin layer, and the bio-based polyurethane is the core layer.

[0006] As an achievable manner, the mass percentage of silver ions in the bio-based polyurethane modified with silver ions is 8%-12%.

[0007] As an achievable manner, the bio-based polyester includes one or more of the following: ethylene 2,5-furandicarboxylate, polytrimethylene terephthalate, or poly(terephthalic acid) multi-component glycol ester, wherein the relative viscosity of the bio-based polyester is in the range of 1.2-2.0.

[0008] As an achievable method, the method further comprises the steps of: preparing polyporphyrin, Specifically, the method comprises: adding pyrrole, para-dicarboxylic acid and propionic acid into a polytetrafluoroethylene-lined autoclave according to certain components by a coprecipitation method, reacting at a set temperature for a set time, performing a hydrothermal treatment, cooling the autoclave to room temperature, filtering, washing, drying the obtained precipitate, or polyporphyrin.

[0009] As an achievable method, the silver acetate and the polyporphyrin are dissolved in N,N-dimethylformamide.

[0010] As an achievable manner, the weight ratio of the polyporphyrin powder loaded with silver ions to the bio-based polyurethane is (10-20): (80-90).

[0011] As an achievable manner, the mass ratio of the skin layer to the core layer feed is 2:8.

[0012] In a second aspect, a bio-based antibacterial monofilament prepared according to the above-mentioned bio-based antibacterial monofilament preparation method is provided, wherein the diameter of the monofilament is 0.2-0.5 mm.

[0013] According to the technical solution provided in the embodiment of the present application, silver ions are loaded by polyporphyrin, because polyporphyrin is co-constructed by organic linkers through covalent bonds, and has excellent stability, high surface area and large voids. When silver ions are coordinated to the polyporphyrin carrier, the silver ions have good dispersibility and are not easy to fall off, and the antibacterial effect can be maintained for a long time, and the antibacterial time can be extended; In addition, the monofilament component in this embodiment is prepared by bio-based polyurethane, the polyporphyrin loaded with silver ions and the bio-based polyurethane are extruded and granulated by a twin-screw extruder, and the polyporphyrin loaded with silver ions is embedded in the bio-based polyurethane. Due to the good compatibility between polyporphyrin and polyurethane, the precipitation of silver ions can be effectively controlled, so that the silver ions in the prepared monofilament can be precipitated stably and for a long time, so that the monofilament has a long-lasting antibacterial effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Other features, objects and advantages of the present application will become more apparent by reading the detailed description of non-limiting embodiments made with reference to the following drawings: Figure 1 This is a flow chart of the method for preparing bio-based antibacterial monofilament in this embodiment. DETAILED DESCRIPTION

[0015] The present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It is to be understood that the specific embodiments described herein are only used to explain the relevant invention, rather than to limit the invention. It is also necessary to explain that, for ease of description, only the parts related to the invention are shown in the accompanying drawings.

[0016] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0017] Please refer to Figure 1 This embodiment provides a method for preparing a bio-based antibacterial monofilament, the method comprising: S10: preparing polyporphyrin loaded with silver ions: providing polyporphyrin, dissolving silver acetate and the polyporphyrin under certain conditions, obtaining unreduced polyporphyrin loaded with silver ions, reducing the unreduced polyporphyrin loaded with silver ions with hydrogen, and obtaining polyporphyrin loaded with silver ions, wherein the mass percentage of silver ions is 8-12%; S20: preparing a bio-based polyurethane modified with polyporphyrin loaded with silver ions: grinding the polyporphyrin loaded with silver ions into powder, adding the powder and the bio-based polyurethane into a twin-screw extruder according to a certain mass ratio for extrusion granulation, wherein the mass percentage of the polyporphyrin loaded with silver ions is 10%-20%, and obtaining bio-based polyurethane particles modified with polyporphyrin loaded with silver ions; S30: Preparation of bio-based antibacterial monofilaments: adding the bio-based polyporphyrin-modified bio-based polyurethane loaded with silver ions and the bio-based polyester into a single screw extruder for extrusion spinning to obtain bio-based antibacterial monofilaments, wherein the bio-based antibacterial monofilaments are of a skin-core structure, the bio-based polyporphyrin-modified bio-based polyurethane loaded with silver ions is the skin layer, and the bio-based polyurethane is the core layer.

[0018] In the preparation process of the monofilament in this embodiment, the silver ions are loaded by polyporphyrin, because polyporphyrin is co-constructed by organic linkers through covalent bonds, and has excellent stability, high surface area and large voids. When the silver ions are coordinated to the polyporphyrin carrier, the silver ions have good dispersibility and are not easy to fall off, and the antibacterial effect can be maintained for a long time, and the antibacterial time can be extended; In addition, the monofilament component in this embodiment is prepared by bio-based polyurethane, the polyporphyrin loaded with silver ions and the bio-based polyurethane are extruded and granulated by a twin-screw extruder, and the polyporphyrin loaded with silver ions is embedded in the bio-based polyurethane. Due to the good compatibility between polyporphyrin and polyurethane, the precipitation of silver ions can be effectively controlled, so that the silver ions in the prepared monofilament can be precipitated stably and for a long time, so that the monofilament has a long-lasting antibacterial effect.

[0019] Wherein, the mass percentage of silver ions in the bio-based polyurethane modified with polyporphyrin loaded with silver ions is 8%-12%.

[0020] The silver ion content in this embodiment is set moderately, so that the prepared monofilament has a good antibacterial effect and can be released for a long time, so that the monofilament has a long-lasting and stable antibacterial effect.

[0021] In this embodiment, silver ions are coordinated to polyporphyrin to improve the dispersibility and stability of silver ions, wherein the polyporphyrin can be prepared by the following steps: Specifically, the method comprises: adding pyrrole, para-dicarboxylic acid and propionic acid into a polytetrafluoroethylene-lined autoclave according to certain components by a coprecipitation method, reacting at a set temperature for a set time, performing a hydrothermal treatment, cooling the autoclave to room temperature, filtering, washing, drying the obtained precipitate, or polyporphyrin.

[0022] Among them, the coprecipitation method can be selected to add pyrrole (5.0 g) and terephthalaldehyde (5.0 g) and propionic acid (150 mL) into a 200 mL polytetrafluoroethylene-lined autoclave, react at 70 ° C for 6 h, and then hydrothermally treat at 120 ° C for 12 h. After the autoclave is cooled to room temperature, the obtained dark brown precipitate is filtered and washed with deionized water. Then it is dried at 80 ° C for 12 h to obtain polyporphyrin.

[0023] In this embodiment, a bio-based polyurethane modified with polyporphyrin loaded with silver ions is used as the cortex material, and a bio-based polyester is used as the core material. The extrusion is carried out through a twin-screw extruder. The silver ions in the cortex can be slowly and stably precipitated, so that the monofilament structure has long-lasting and stable antibacterial properties. In addition, the skin-core structure of the entire monofilament is a biomass product, which has advantages in carbon emission reduction and can effectively reduce the impact on the environment. The bio-based polyurethane in this embodiment is a biomedical polyurethane, which has good degradability and can be recycled as a whole, with good economic, environmental and social benefits.

[0024] Optionally, the bio-based polyester includes one or more of the following: ethylene 2,5-furandicarboxylate, polytrimethylene terephthalate, or poly(trimethylene terephthalate) multi-component glycol ester, wherein the relative viscosity of the bio-based polyester is in the range of 1.2-2.0.

[0025] Optionally, the silver acetate and the polyporphyrin are dissolved in N,N-dimethylformamide.

[0026] Optionally, the weight ratio of the silver ion-loaded polyporphyrin powder to the bio-based polyurethane is (10-20): (80-90); The mass ratio of the skin layer to the core layer feed is 2:8.

[0027] The materials of the skin layer and the core layer are extruded through a single screw extruder using a skin-core spinning method, wherein the temperatures of the various zones in the single screw extruder are 280°C / 290°C / 290°C in sequence, followed by cooling, stretching, heat setting and winding, wherein the cooling method is water cooling, and the cooling temperature is 26°C; the stretching adopted is a two-stage stretching process, wherein the primary stretching temperature is 80°C, the stretching ratio is 3-5 times, the secondary stretching temperature is 150°C, and the stretching ratio is 1.2-1.6 times; the final heat setting temperature is about 155°C, and hot air setting is preferably used.

[0028] This embodiment also provides a bio-based antibacterial monofilament prepared by the above preparation method, wherein the diameter of the monofilament is 0.2-0.5 mm.

[0029] According to the above method, five embodiments are given below, which respectively test the change of silver ion concentration and the antibacterial rate in different embodiments, thereby demonstrating the antibacterial ability of the monofilament in different embodiments. Among them, the silver ion concentration and the antibacterial performance are tested by agar diffusion method and carrier immersion quantitative method.

[0030] Example 1 Step 1: Pyrrole (5.0 g), terephthalaldehyde (5.0 g) and propionic acid (150 mL) were added to a 200 mL polytetrafluoroethylene-lined autoclave by coprecipitation, reacted at 70 °C for 6 h, and then hydrothermally treated at 120 °C for 12 h. After the autoclave was cooled to room temperature, the dark brown precipitate was filtered and washed with deionized water. Then it was dried at 80 °C for 12 h to obtain polyporphyrin. Then silver acetate (0.32 g) and polyporphyrin (2.0 g) were dissolved in N,N-dimethylformamide (100 mL) and refluxed at 150 °C for 8 h. After the mixture was cooled to room temperature, unreduced polyporphyrin loaded with silver ions was obtained and recovered by filtration. After being thoroughly washed with deionized water, it was dried overnight at 60 °C. Finally, the polyporphyrin loaded with silver ions was obtained by reduction with hydrogen at 300 °C. The mass percentage of silver ions in the polyporphyrin loaded with silver ions was 10%. Step 2: The silver ion-loaded polyporphyrin prepared in step 1 is dried and ground into powder, and the silver ion-loaded polyporphyrin powder and bio-based polyurethane are added into a twin-screw extruder at a mass fraction ratio of 10:90, and granulated by extrusion through the twin-screw extruder at an extruder temperature of 130-180° C. to obtain a bio-based polyurethane modified with silver ions; Step 3: The silver ion-loaded polyporphyrin-modified bio-based polyurethane and 2,5-furandicarboxylic acid ethylene glycol prepared in step 2 are extruded by a single screw extruder at 280 ℃ / 290 ℃ / 290 ℃ using a skin-core spinning method, cooled, stretched, heat-set, and rolled to obtain a skin-core structured bio-based antibacterial composite monofilament, wherein the bio-based polyester is the core layer, and the silver ion-loaded polyporphyrin-modified bio-based polyurethane is the skin layer, and the mass ratio of the skin layer to the core layer is 2:8. The cooling method is water cooling, and the cooling temperature is 26 ℃. The stretching adopts a two-stage stretching process, wherein the primary stretching temperature is 80 ℃, the stretching ratio is 3 times, the secondary stretching temperature is 150 ℃, the stretching ratio is 1.2 times, and the heat setting temperature is 155 ℃. The monofilament diameter is 0.5 mm.

[0031] Example 2 Step 1: Pyrrole (5.0 g), terephthalaldehyde (5.0 g) and propionic acid (150 mL) were added to a 200 mL polytetrafluoroethylene-lined autoclave by coprecipitation, reacted at 70 °C for 6 h, and then hydrothermally treated at 120 °C for 12 h. After the autoclave was cooled to room temperature, the dark brown precipitate was filtered and washed with deionized water. Then it was dried at 80 °C for 12 h to obtain polyporphyrin. Then silver acetate (0.37 g) and polyporphyrin (2.0 g) were dissolved in N,N-dimethylformamide (100 mL) and refluxed at 150 °C for 8 h. After the mixture was cooled to room temperature, unreduced polyporphyrin loaded with silver ions was obtained and recovered by filtration. After being thoroughly washed with deionized water, it was dried overnight at 60 °C. Finally, the polyporphyrin loaded with silver ions was obtained by reduction with hydrogen at 300 °C. The mass percentage of silver ions in the polyporphyrin loaded with silver ions was 12%. Step 2: The silver ion-loaded polyporphyrin prepared in step 1 is dried and ground into powder, and the silver ion-loaded polyporphyrin powder and bio-based polyurethane are added into a twin-screw extruder at a mass fraction ratio of 10:90, and granulated by extrusion through the twin-screw extruder at an extruder temperature of 130-180° C. to obtain a bio-based polyurethane modified with silver ions; Step 3: The silver ion-loaded polyporphyrin-modified bio-based polyurethane and polytrimethylene terephthalate prepared in step 2 are extruded by a single screw extruder at 280°C / 290°C / 290°C by a skin-core spinning method, cooled, stretched, heat-set, and rolled to obtain a skin-core structured bio-based antibacterial composite monofilament, wherein the bio-based polyester is the core layer, and the silver ion-loaded polyporphyrin-modified bio-based polyurethane is the skin layer, and the mass ratio of the skin layer to the core layer is 2:8. The cooling method is water cooling, and the cooling temperature is 26°C. The stretching adopts a two-stage stretching process, wherein the primary stretching temperature is 80°C, the stretching ratio is 3 times, the secondary stretching temperature is 150°C, the stretching ratio is 1.6 times, and the heat setting temperature is 155°C. The monofilament diameter is 0.4mm.

[0032] Example 3 Step 1: Pyrrole (5.0 g), terephthalaldehyde (5.0 g) and propionic acid (150 mL) were added to a 200 mL polytetrafluoroethylene-lined autoclave by coprecipitation, reacted at 70 °C for 6 h, and then hydrothermally treated at 120 °C for 12 h. After the autoclave was cooled to room temperature, the dark brown precipitate was filtered and washed with deionized water. Then it was dried at 80 °C for 12 h to obtain polyporphyrin. Then silver acetate (0.25 g) and polyporphyrin (2.0 g) were dissolved in N,N-dimethylformamide (100 mL) and refluxed at 150 °C for 8 h. After the mixture was cooled to room temperature, unreduced polyporphyrin loaded with silver ions was obtained and recovered by filtration. After being thoroughly washed with deionized water, it was dried overnight at 60 °C. Finally, the polyporphyrin loaded with silver ions was obtained by reduction with hydrogen at 300 °C. The mass percentage of silver ions in the polyporphyrin loaded with silver ions was 8%. Step 2: The silver ion-loaded polyporphyrin prepared in step 1 is dried and ground into powder, and the silver ion-loaded polyporphyrin powder and bio-based polyurethane are added into a twin-screw extruder at a mass fraction ratio of 20:80, and granulated by extrusion through the twin-screw extruder at an extruder temperature of 130-180° C. to obtain a bio-based polyurethane modified with silver ions; Step 3: The silver ion-loaded polyporphyrin-modified bio-based polyurethane and polytrimethylene terephthalate prepared in step 2 are extruded by a single screw extruder at 280 ℃ / 290 ℃ / 290 ℃ using a skin-core spinning method, cooled, stretched, heat-set, and rolled to obtain a skin-core structured bio-based antibacterial composite monofilament, wherein the bio-based polyester is the core layer, and the silver ion-loaded polyporphyrin-modified bio-based polyurethane is the skin layer, and the mass ratio of the skin layer to the core layer is 2:8. The cooling method is water cooling, and the cooling temperature is 26 ℃. The stretching adopts a two-stage stretching process, wherein the primary stretching temperature is 80 ℃, the stretching ratio is 4 times, the secondary stretching temperature is 150 ℃, the stretching ratio is 1.4 times, and the heat setting temperature is 155 ℃. The monofilament diameter is 0.35 mm.

[0033] Example 4 Step 1: Pyrrole (5.0 g), terephthalaldehyde (5.0 g) and propionic acid (150 mL) were added to a 200 mL polytetrafluoroethylene-lined autoclave by coprecipitation, reacted at 70 °C for 6 h, and then hydrothermally treated at 120 °C for 12 h. After the autoclave was cooled to room temperature, the dark brown precipitate was filtered and washed with deionized water. Then it was dried at 80 °C for 12 h to obtain polyporphyrin. Then silver acetate (0.32 g) and polyporphyrin (2.0 g) were dissolved in N,N-dimethylformamide (100 mL) and refluxed at 150 °C for 8 h. After the mixture was cooled to room temperature, unreduced polyporphyrin loaded with silver ions was obtained and recovered by filtration. After being thoroughly washed with deionized water, it was dried overnight at 60 °C. Finally, the polyporphyrin loaded with silver ions was obtained by reduction with hydrogen at 300 °C. The mass percentage of silver ions in the polyporphyrin loaded with silver ions was 10%. Step 2: The silver ion-loaded polyporphyrin prepared in step 1 is dried and ground into powder, and the silver ion-loaded polyporphyrin powder and bio-based polyurethane are added into a twin-screw extruder at a mass fraction ratio of 20:80, and granulated by extrusion through the twin-screw extruder at an extruder temperature of 130-180° C. to obtain a bio-based polyurethane modified with silver ions; Step 3: The silver ion-loaded polyporphyrin-modified bio-based polyurethane and polyterephthalic acid multi-component diol ester prepared in step 2 are extruded by a single screw extruder at 280 ℃ / 290 ℃ / 290 ℃ using a skin-core spinning method, cooled, stretched, heat-set, and rolled to obtain a skin-core structure bio-based antibacterial composite monofilament, the bio-based polyester is the core layer, the silver ion-loaded polyporphyrin-modified bio-based polyurethane is the skin layer, and the mass ratio of the skin layer to the core layer is 2:8. The cooling method is water cooling, and the cooling temperature is 26 ℃. The stretching adopts a two-stage stretching process, wherein the primary stretching temperature is 80 ℃, the stretching ratio is 5 times, the secondary stretching temperature is 150 ℃, the stretching ratio is 1.2 times, and the heat setting temperature is 155 ℃. The monofilament diameter is 0.3 mm.

[0034] Example 5 Step 1: Pyrrole (5.0 g), terephthalaldehyde (5.0 g) and propionic acid (150 mL) were added to a 200 mL polytetrafluoroethylene-lined autoclave by coprecipitation, reacted at 70 °C for 6 h, and then hydrothermally treated at 120 °C for 12 h. After the autoclave was cooled to room temperature, the dark brown precipitate was filtered and washed with deionized water. Then it was dried at 80 °C for 12 h to obtain polyporphyrin. Then silver acetate (0.37 g) and polyporphyrin (2.0 g) were dissolved in N,N-dimethylformamide (100 mL) and refluxed at 150 °C for 8 h. After the mixture was cooled to room temperature, unreduced polyporphyrin loaded with silver ions was obtained and recovered by filtration. After being thoroughly washed with deionized water, it was dried overnight at 60 °C. Finally, the polyporphyrin loaded with silver ions was obtained by reduction with hydrogen at 300 °C. The mass percentage of silver ions in the polyporphyrin loaded with silver ions was 12%. Step 2: The silver ion-loaded polyporphyrin prepared in step 1 is dried and ground into powder, and the silver ion-loaded polyporphyrin powder and bio-based polyurethane are added into a twin-screw extruder at a mass fraction ratio of 20:80, and granulated by extrusion through the twin-screw extruder at an extruder temperature of 130-180° C. to obtain a bio-based polyurethane modified with silver ions; Step 3: The silver ion-loaded polyporphyrin-modified bio-based polyurethane and polyterephthalic acid multi-component diol ester prepared in step 2 are extruded by a single screw extruder at 280 ℃ / 290 ℃ / 290 ℃ using a skin-core spinning method, cooled, stretched, heat-set, and rolled to obtain a skin-core structured bio-based antibacterial composite monofilament, wherein the bio-based polyester is the core layer, and the silver ion-loaded polyporphyrin-modified bio-based polyurethane is the skin layer, and the mass ratio of the skin layer to the core layer is 2:8. The cooling method is water cooling, and the cooling temperature is 26 ℃. The stretching adopts a two-stage stretching process, wherein the primary stretching temperature is 80 ℃, the stretching ratio is 5 times, the secondary stretching temperature is 150 ℃, the stretching ratio is 1.6 times, and the heat setting temperature is 155 ℃. The monofilament diameter is 0.2 mm.

[0035] Comparative Example Step 1: Preparation of bio-based polyurethane loaded with silver ions Adding nanosilver with a particle size of 50 nm and bio-based polyurethane in a mass fraction ratio of 1:99 into a twin-screw extruder, extruding and granulating through the twin-screw extruder at an extruder temperature of 130-180°C, to obtain bio-based polyurethane loaded with silver ions; Step 2: Preparation of bio-based antibacterial composite monofilament The silver ion-loaded polyporphyrin-modified bio-based polyurethane and 2,5-furandicarboxylic acid ethylene glycol prepared in step 2 are extruded by a single screw extruder at 280 ℃ / 290 ℃ / 290 ℃ by a skin-core spinning method, cooled, stretched, heat-set, and rolled to obtain a bio-based antibacterial composite monofilament with a skin-core structure, wherein the bio-based polyester is the core layer, the silver ion-loaded bio-based polyurethane is the skin layer, and the mass ratio of the skin layer to the core layer is 2:8. The cooling method is water cooling, and the cooling temperature is 26 ℃. The stretching adopts a two-stage stretching process, wherein the primary stretching temperature is 80 ℃, the stretching ratio is 3 times, the secondary stretching temperature is 150 ℃, the stretching ratio is 1.2 times, and the heat setting temperature is 155 ℃. The monofilament diameter is 0.5 mm.

[0036] Table 1 Changes of silver ion concentration over time Table 2 Antibacterial rate of bio-based antibacterial composite monofilament According to Table 1: Comparison of the embodiments and comparative examples, it can be seen that after silver and polyporphyrin are loaded, the silver ions in the fiber are evenly released, while in the comparative example, since silver is not loaded with polyporphyrin, the silver ions are released quickly in the early stage and the silver ion release rate decreases in the later stage, indicating that after silver and polyporphyrin are loaded, the purpose of sustained release is achieved and the antibacterial effect of the monofilament is prolonged.

[0037] According to Table 2, the monofilaments provided in the examples can have a good inhibitory effect on the above-mentioned bacteria.

[0038] It should be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like used above to indicate orientations or positional relationships are based on the orientations or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention; the orientation words "inside" and "outside" refer to the inside and outside relative to the contours of the components themselves. In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.

[0039] The above description is only a preferred embodiment of the present application and an explanation of the technical principles used. Those skilled in the art should understand that the scope of the invention involved in the present application is not limited to the technical solution formed by a specific combination of the above technical features, but should also cover other technical solutions formed by any combination of the above technical features or their equivalent features without departing from the inventive concept. For example, the above features are replaced with (but not limited to) technical features with similar functions disclosed in the present application.

Claims

1. A method for preparing a bio-based antibacterial monofilament, characterized in that: The method comprises: Preparation of polyporphyrin loaded with silver ions: providing polyporphyrin, dissolving silver acetate and the polyporphyrin under certain conditions, obtaining unreduced polyporphyrin loaded with silver ions, reducing the unreduced polyporphyrin loaded with silver ions with hydrogen, and obtaining polyporphyrin loaded with silver ions, wherein the mass percentage of silver ions is 8-12%; Preparation of silver ion-loaded polyporphyrin-modified bio-based polyurethane: grinding the silver ion-loaded polyporphyrin into powder, adding the powder and the bio-based polyurethane into a twin-screw extruder according to a certain mass ratio for extrusion granulation, wherein the mass percentage of the silver ion-loaded polyporphyrin is 10%-20%, and obtaining silver ion-loaded polyporphyrin-modified bio-based polyurethane particles; Preparation of bio-based antibacterial monofilament: adding the bio-based polyporphyrin-modified bio-based polyurethane loaded with silver ions and bio-based polyester into a single-screw extruder for extrusion spinning to obtain the bio-based antibacterial monofilament, wherein the bio-based antibacterial monofilament is a skin-core structure, the bio-based polyporphyrin-modified bio-based polyurethane loaded with silver ions is the skin layer, and the bio-based polyurethane is the core layer.

2. The method for preparing bio-based antibacterial monofilament according to claim 1, characterized in that: The mass percentage of silver ions in the bio-based polyurethane modified with polyporphyrin loaded with silver ions is 8%-12%.

3. The method for preparing the bio-based antibacterial monofilament according to claim 1, characterized in that: The bio-based polyester includes one or more of the following: ethylene 2,5-furandicarboxylate, polytrimethylene terephthalate, or poly(terephthalate) multi-component glycol ester, wherein the relative viscosity of the bio-based polyester is in the range of 1.2-2.

0.

4. The method for preparing the bio-based antibacterial monofilament according to claim 1, characterized in that: The method further comprises the steps of: preparing polyporphyrin, Specifically, the method comprises: adding pyrrole, para-dicarboxylic acid and propionic acid into a polytetrafluoroethylene-lined autoclave according to certain components by a coprecipitation method, reacting at a set temperature for a set time, performing a hydrothermal treatment, cooling the autoclave to room temperature, filtering, washing, drying the obtained precipitate, or polyporphyrin.

5. The method for preparing bio-based antibacterial monofilament according to claim 1, characterized in that: The silver acetate and the polyporphyrin are dissolved in N,N-dimethylformamide.

6. The method for preparing the bio-based antibacterial monofilament according to claim 1, characterized in that: The mass ratio of the silver ion-loaded polyporphyrin powder to the bio-based polyurethane is (10-20): (80-90).

7. The method for preparing the bio-based antibacterial monofilament according to claim 1, characterized in that: The mass ratio of the skin layer to the core layer feed is 2:

8.

8. A bio-based antibacterial monofilament prepared by the method for preparing a bio-based antibacterial monofilament according to any one of claims 1 to 7, wherein the diameter of the monofilament is 0.2-0.5 mm.

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