Preparation and Application of Copper-Based Microspheres and Antibacterial Fibers Using the Same as Raw Materials

Abstract

The present invention relates to the technical field of antibacterial fibers, and particularly to the preparation and application of copper-based microspheres and antibacterial fibers using the same as a raw material. The copper-based antibacterial fiber is obtained by melt spinning after uniformly mixing an antibacterial polymer powder and a polymer. The antibacterial polymer powder has a core-shell structure; the antibacterial polymer powder has a polymer as the core and a copper-based microsphere antibacterial agent as the shell; the loading amount of the copper-based microsphere antibacterial agent in the antibacterial polymer powder is 20 wt%; the copper-based microsphere antibacterial agent is a composite microsphere structure of Cu nanocrystals and Cu2O nanocrystals. The copper-based antibacterial fiber prepared by the present invention has strong antibacterial properties and good biocompatibility, and can be widely applied to fields such as household textiles, medical gauze, military training uniforms, filter meshes, fishing nets, etc.; from the perspective of material preparation, the present invention solves the extremely high requirement for the dispersibility of antibacterial agents in the melt spinning method, filling the technical gap in this aspect.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial fibers, and particularly to the preparation and application of copper-based microspheres and antibacterial fibers using the same as a raw material. Background Art

[0002] Harmful bacteria can cause various diseases and pose a threat to human health. Clothing is an item that people must come into contact with every day. The sweat excreted by the human body provides sufficient moisture and grease for the reproduction of bacteria. Ordinary textile fibers do not have antibacterial ability, and bacteria are likely to grow on the skin surface, which will not only produce bad smells but also pose a threat to health. In addition, textile products such as filter meshes and fishing nets are exposed to a bacterial environment with water for a long time, and are severely corroded by bacteria, which is likely to cause the attachment of fouling organisms, greatly limiting their service life. It is urgent to develop textile industrial and agricultural products with antibacterial functions. Copper nanomaterials have been proven to have excellent antibacterial activity. Using nano-copper as an antibacterial agent to carry out antibacterial modification on polymer fibers to prepare polymer fibers with antibacterial efficacy has broad application prospects.

[0003] Currently, most studies prepare antibacterial fibers by post-treatment methods. On the obtained fibers, the antibacterial agent is loaded onto the fiber surface by physical adsorption, chemical chelation or grafting. The antibacterial fibers prepared in this way have poor binding force between the antibacterial agent and the fiber matrix, and insufficient washing resistance and durability. For example, Patent CN101942759A immerses the prefabricated fibers in a silver nitrate solution to adsorb silver ions, and then adds a reducing agent to reduce the silver ions on the fiber surface to nano-silver particles, thereby obtaining nano-silver antibacterial fibers. The antibacterial fibers prepared by this method have poor washing resistance and durability, and a short service life.

[0004] The antibacterial masterbatch is made into antibacterial fibers by the process of melt spinning. The antibacterial agent can be embedded inside the fibers, so that the antibacterial agent is firmly locked in the linear grid composed of polymer macromolecules, and the long-term and durable use of antibacterial and antiviral fibers can be achieved. Usually, the aperture of the spinneret for melt spinning is between 15 and 36 μm. To successfully draw the wire and ensure good mechanical properties of the fibers, the particle size of the antibacterial agent is at least submicron and has good dispersibility. Therefore, this technology has extremely high requirements for the dispersibility and particle size of the antibacterial agent in the antibacterial masterbatch. Patent CN105332088A adsorbs Cu(OH)2 gel into the pores of mesoporous zirconium phosphate to obtain a precursor of copper oxide@mesoporous zirconium phosphate, and adds it to a mixed solution of terephthalic acid and diol. A nano-copper oxide / polyester-based composite antibacterial masterbatch is prepared by in-situ polymerization, and then antibacterial fibers are prepared by melt spinning. Although antibacterial fibers are prepared by using the monodisperse characteristics of mesoporous zirconium phosphate for spinning, due to the small content of its antibacterial functional components, the antibacterial activity and long-term effectiveness are insufficient, and the in-situ polymerization process is complex and the reaction conditions are difficult to control, which is not suitable for industrial production.

[0005] Therefore, it is of great significance to provide a copper-based antibacterial fiber with a simple preparation method, high antibacterial activity, long-term effectiveness, and good stability for the field of antibacterial fiber technology. Summary of the Invention

[0006] Based on the above, the present invention provides a preparation and application of copper-based microspheres and antibacterial fibers using the same as raw materials. The copper-based antibacterial fibers have the advantages of high antibacterial activity, long-term effectiveness, and good stability.

[0007] To achieve the above object, the present invention provides the following solutions:

[0008] One of the technical solutions of the present invention is an antibacterial polymer powder with a core-shell structure; the antibacterial polymer powder uses a polymer as the core and a copper-based microsphere antibacterial agent (Cu / Cu2O composite microspheres) as the shell; the loading amount of the copper-based microsphere antibacterial agent in the antibacterial polymer powder is 20 wt%.

[0009] The copper-based microsphere antibacterial agent is a composite microsphere structure of Cu nanocrystals and Cu2O nanocrystals, with an average particle size of 100 - 600 nm;

[0010] The polymer is at least one of polyethylene terephthalate (PET), polyamide (PA), polyethylene (PE), polyurethane (PU), polypropylene (PP), and polyvinyl chloride (PVC).

[0011] The Cu / Cu2O composite microspheres exhibit monodisperse characteristics.

[0012] The antibacterial polymer powder of the present invention uniformly loads monodisperse Cu / Cu2O composite microspheres on the surface of polymer particles. The heterojunction formed by Cu nanocrystals and Cu2O nanocrystals endows it with efficient photocatalytic properties, promoting the generation of ROS (reactive oxygen species). The ROS reacts with Cu 2+ to have a synergistic bactericidal effect, achieving a strong antibacterial effect; moreover, this core-shell structure can effectively improve the dispersion compatibility of Cu / Cu2O composite microspheres in the polymer fiber matrix, thereby endowing the antibacterial fiber with good mechanical properties; the present invention discovers that when the Cu / Cu2O composite microspheres are within a certain loading range, it can not only ensure the production efficiency of the copper-based microsphere antibacterial agent but also prevent the phenomenon of insufficient surface active sites on the polymer particles. When the loading amount is too low, the yield of the copper-based microsphere antibacterial agent is low, which is not conducive to industrial production; when the loading amount is too high, there are not enough surface active sites on the polymer particles, and there may be a problem of secondary aggregation of the copper-based microsphere antibacterial agent; the Cu / Cu2O composite microspheres in the copper-based antibacterial fiber of the present invention are monodisperse, with controllable particle size, and the average size is 100 - 600 nm, effectively improving the dispersion compatibility of Cu / Cu2O composite microspheres in the polymer matrix.

[0013] The second technical solution of the present invention is a preparation method of the above-mentioned antibacterial polymer powder, which includes the following steps:

[0014] Polyvinylpyrrolidone and a polymer are successively added to an ethylene glycol solution, and then a divalent copper salt, an alkali solution, and glucose are successively added, and reacted to obtain the antibacterial polymer powder.

[0015] The relative molecular weight of the polyvinylpyrrolidone is 360000 - 1300000; the purpose of adding polyvinylpyrrolidone is to perform surface modification on the polymer.

[0016] The alkali solution needs to be added slowly. The purpose of adding the alkali solution is to form a Cu(OH)2 colloid.

[0017] The purpose of adding glucose is to reduce Cu 2+ to Cu nanocrystals and Cu2O nanocrystals. By changing the addition amount of glucose, the content of the Cu phase in the Cu / Cu2O composite microspheres can be regulated. The larger the addition amount of glucose, the higher the content of the Cu phase. If the addition amount is too high, the content of Cu2O will be less, and the photocatalytic response will be poor; if the addition amount is too low, the content of the Cu phase is insufficient, the number of heterojunctions is small, and the photocatalytic efficiency is low.

[0018] Furthermore, the divalent copper salt is at least one of copper chloride, copper sulfate, copper nitrate, and copper acetate; the alkali solution is a 12 mol / L NaOH solution.

[0019] Further, the temperature of the reaction is 55 to 80 °C, and the time is 10 to 20 min.

[0020] Further, the volume-mass ratio of the ethylene glycol, polyvinylpyrrolidone, high molecular polymer, divalent copper salt, alkali solution and glucose is 50 L: 2.5 kg: 2 to 8 kg: 1 to 6 kg: 3 to 13 L: 0.3 to 4 kg.

[0021] The third technical solution of the present invention is the application of the above antibacterial high molecular polymer powder in the preparation of antibacterial fibers.

[0022] The fourth technical solution of the present invention is a copper-based antibacterial fiber, which uses the above antibacterial high molecular polymer powder as the antibacterial component of the fiber.

[0023] The present invention uses the Cu / Cu2O composite microspheres in the antibacterial high molecular polymer powder as the effective antibacterial component of the fiber.

[0024] The fifth technical solution of the present invention is a preparation method of the above copper-based antibacterial fiber, which includes the following steps:

[0025] Mix the above antibacterial high molecular polymer powder with the high molecular polymer evenly and then melt-spin to obtain the copper-based antibacterial fiber; in this technical solution, the high molecular polymer is in powder form and the same high molecular polymer as that used in the preparation of the antibacterial high molecular polymer powder is adopted.

[0026] Further, by mass percentage, the addition amount of the antibacterial high molecular polymer powder is 0.5 wt% to 5 wt% (the specific addition amount can refer to the proportion of the antibacterial fiber in the actual product); the content of the copper-based microsphere antibacterial agent in the copper-based antibacterial fiber is 0.1 wt% to 1 wt%.

[0027] The sixth technical solution of the present invention is the application of the above copper-based antibacterial fiber in the preparation of household textiles, medical gauze, military training uniforms, filter meshes or fishing nets.

[0028] The present invention discloses the following technical effects:

[0029] (1) The present invention uses the self-assembly effect of ethylene glycol to prepare Cu / Cu2O composite microspheres. The spherical Cu / Cu2O composite microspheres have excellent Cu 2+ sustained-release performance. At the same time, the Cu / Cu2O heterojunction endows it with high photocatalytic characteristics, promotes the generation of ROS reactive oxygen species, and 2+ synergizes with Cu

[0030] (2) The present invention uses PVP to conduct surface chemical modification on polymer particles. By adopting the in-situ growth technique, monodisperse Cu / Cu2O composite microspheres are uniformly loaded on the surface of the polymer particles. The particle size is controllable, and the average size is in the range of 100 - 600 nm. This method effectively improves the dispersion compatibility of the Cu / Cu2O composite microspheres (copper-based microsphere antibacterial agents) in the polymer fiber matrix, solves the agglomeration problem in the large-scale preparation of nano-antibacterial agents, and enables the antibacterial fibers obtained after melt spinning to have good mechanical properties.

[0031] (3) The present invention prepares antibacterial polymer powder by the solution method. The reaction conditions are mild, the preparation process is simple, the yield is high, and the repeatability is good, showing broad industrialization prospects. The copper-based antibacterial fibers prepared by the present invention have strong antibacterial properties, and the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are > 99%. They have good biocompatibility and are non-toxic to L929 mouse fibroblasts. They can be widely applied to fields such as household textiles, medical gauze, military training uniforms, filter meshes, fishing nets, etc., and have good application prospects.

[0032] (4) From the perspective of material preparation, the present invention solves the extremely high requirement for the dispersibility of antibacterial agents in the melt spinning method, filling the technical gap in this aspect. Description of the Drawings

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0034] Figure 1 SEM photographs of the PET powder in step 1 of Example 1 and the antibacterial PET powder loaded with Cu / Cu2O composite microspheres; among them, (a) represents the PET powder, and (b), (c), and (d) are SEM photographs of the antibacterial PET powder at different magnification ratios.

[0035] Figure 2 TEM photograph and high-resolution transmission electron microscope photograph of the Cu / Cu2O composite microspheres in step 1 of Example 1; among them, (a) is the TEM photograph, and (b), (c), and (d) are high-resolution transmission electron microscope photographs.

[0036] Figure 3 Photograph of the plate colony count in the antibacterial test of the polyester-cotton blended fiber fabric in Example 1.

[0037] Figure 4Morphological photograph of L929 mouse fibroblasts in the cytotoxicity test of the polyester-cotton blended fiber fabric in Example 1. Detailed implementation mode

[0038] The various exemplary implementation modes of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and implementation schemes of the present invention.

[0039] It should be understood that the terms described in the present invention are only for describing specific implementation modes and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0040] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0041] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific implementation modes of the present invention specification, which are obvious to those skilled in the art. Other implementation modes obtained from the present invention specification are obvious to those skilled in the art. The present invention specification and examples are only exemplary.

[0042] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0043] The present invention explores the surface chemical modification of polymer powder particles and the dispersion compatibility technology of copper-based microsphere antibacterial agents (Cu / Cu2O composite microspheres) on their surfaces. By coating PVP on the surface of polymer particles, which serves as the nucleation site for Cu / Cu2O composite microspheres, monodisperse Cu / Cu2O composite microspheres are uniformly loaded on their surfaces through in-situ growth. This antibacterial polymer powder is blended and stirred evenly with the same polymer according to a certain mass ratio, and then melt-spun to obtain copper-based antibacterial fibers. The polymer particles include at least one of polyethylene terephthalate, polyamide, polyethylene, polyurethane, polypropylene, and polyvinyl chloride. In the embodiments of the present invention, PET and PA6 with the best selection effect are typically but not restrictively selected as examples.

[0044] In the embodiments of the present invention, the raw materials used, unless otherwise specified, can be obtained through commercial channels.

[0045] The PET and PA6 powders used in the embodiments of the present invention are both of spinning grade, with a particle size of about 100 μm.

[0046] The relative molecular mass of polyvinylpyrrolidone (PVP) used in the embodiments of the present invention is 360,000.

[0047] The test methods involved in the present invention:

[0048] Antibacterial test: According to Appendix B of "GB / T 21510-2008 Test Method for Antibacterial Properties of Nano-inorganic Materials", cut the antibacterial fabric into 10 mm * 10 mm and put it into a triangular flask. At the same time, prepare a pure cotton plain white cloth of the same size as the control group. Add 95 mL of PBS and mix well, then add 5 mL of pre-prepared bacterial suspension. Oscillate and contact at 37 °C and 150 r / min for 18 h. After appropriate dilution, take 1 mL of the sample solution and spread it on the nutrient agar medium. After culturing at 37 °C for 48 h, perform colony counting and calculate the antibacterial rate.

[0049] Cytotoxicity test: According to the MTT method in Appendix C of "GB / T 16886.5-2017 In Vitro Cytotoxicity Test", test the cytotoxicity of the antibacterial fabric. The test cells are L929 mouse fibroblasts. Weigh 2 g of the antibacterial fabric and add it to 20 mL of complete culture medium (mass concentration of 0.1 g / mL), and place it in a 37 °C incubator for extraction for 4 h. Take the cell concentration of 5*10 4The logarithmic growth phase normal cell suspension at a density of cells / mL was added to a 96-well plate, 100 μL per well, and then cultured overnight until the cells adhered to the plate. The next day, the culture medium in each well was removed, and 100 μL of the extract was added to each well. The blank control group was added with a pure culture medium solution, and incubated at 37 °C, 5% CO2, and a humidity of >90% for 24 h. Then, a phase contrast microscope was used to observe the morphological changes of the cells caused by the cytotoxicity of the test sample extract. After the plate inspection, the culture medium was removed, 20 μL of an MTT solution with a concentration of 5 mg / mL was added to each well, and after mixing, the incubation was continued for 2 h. The 96-well plate was inverted and gently shaken dry, 150 μL of dimethyl sulfoxide was added to each well, and after shaking for 10 min to fully dissolve, the absorbance (OD value) was measured at 570 nm using an enzyme-linked immunosorbent assay reader. Finally, the cell survival rate was calculated based on the OD value.

[0050] Example 1

[0051] Step 1: Add 50 L of pure ethylene glycol solution to a 100-L glass reactor, add 2.5 kg of PVP powder with a molecular weight of 360,000 while stirring. After it is completely dissolved, add 2 kg of PET powder and stir for 12 h. Then add 1280 g of CuCl2·H2O, stir until completely dissolved, slowly add 3065 mL of a NaOH solution with a concentration of 12 mol / L, and then add 375 g of anhydrous glucose at 70 °C and react for 15 min; after filtration, washing, and drying, antibacterial PET powder (antibacterial polymer powder) loaded with 20 wt% Cu / Cu2O composite microspheres was obtained. The average particle size of the Cu / Cu2O composite microspheres was about 400 nm.

[0052] Step 2: Mix the above antibacterial PET powder evenly with pure PET powder at an addition amount of 2.5 wt% (i.e., the mass of the antibacterial PET powder accounts for 2.5 wt% of the total mass), control the moisture content to be less than 100 ppm, and melt-spin at 280 °C to produce copper-based antibacterial fibers. The content of Cu / Cu2O composite microspheres in the copper-based antibacterial fibers was 5 wt‰, and the Cu / Cu2O composite microspheres were uniformly dispersed in the copper-based antibacterial fibers.

[0053] The SEM photos of the PET powder and the antibacterial PET powder loaded with Cu / Cu2O composite microspheres in Step 1 of this example are as Figure 1 shown; in the figure, (a) represents the pure PET powder, and (b), (c), and (d) are the SEM photos of the antibacterial PET powder at different magnification ratios. It can be Figure 1 seen that the Cu / Cu2O composite microspheres are uniformly loaded on the surface of the PET particles, forming a core-shell structure of polymer particles (PET) and Cu / Cu2O composite microspheres. The particle size of the Cu / Cu2O composite microspheres is about 400 nm.

[0054] Figure 2 Figure (a) in [X] is the TEM image of the Cu / Cu2O composite microspheres in Step 1 of Example 1. It can be clearly seen from Figure 2 Figure (a) that there are contrast changes inside the microspheres. The dark regions marked by the red circles can be considered as the Cu phase, and the remaining light regions are the Cu2O phase. Figure 2 Figures (b), (c), and (d) in [X] are the high-resolution transmission electron microscopy images. Lattice fringe measurements were performed on the Cu / Cu2O composite microspheres. Figures (c) and (d) are the enlarged images of the regions circled in green and blue in Figure (b), respectively. The lattice plane spacings of d = 0.302 nm and d = 0.246 nm marked in Figures (b) and (d) correspond to the (110) and (111) crystal planes of Cu2O, respectively. The d = 0.209 nm in Figure (c) is the lattice plane spacing of the (111) crystal plane of Cu. This can prove the existence of the Cu / Cu2O heterojunction.

[0055] The copper-based antibacterial fibers prepared in Step 2 of Example 1 were blended with cotton fibers at a ratio of 65:35 to weave a polyester-cotton blended fiber fabric, which can be used to produce antibacterial clothing. According to Appendix B of "GB / T 21510-2008 Test Method for Antibacterial Properties of Nano-inorganic Materials", the antibacterial rates of this polyester-cotton blended fiber fabric against Escherichia coli, Staphylococcus aureus, and Candida albicans were all > 99% (the plate colony count photos of the polyester-cotton blended fiber fabric in the antibacterial test are as shown in Figure 2 Figure [X]). At the same time, according to "GB / T 16886.5-2017 In Vitro Cytotoxicity Test", the cell survival rate of L929 mouse fibroblasts for this polyester-cotton blended fiber fabric was 75.686% (the morphological photos of L929 mouse fibroblasts of the polyester-cotton blended fiber fabric in the cytotoxicity test are as shown in Figure 3 Figure [X]). According to the five-level cytotoxicity classification, it can be determined as a non-cytotoxic product. According to the requirements of "FZ / T 73023-2006 Antibacterial Knitted Fabrics", after washing 50 times, the antibacterial rates of this polyester-cotton blended fiber fabric against Escherichia coli and Staphylococcus aureus still reached 92.8% and 95.3%, respectively. After washing 120 times, the antibacterial rates of this polyester-cotton blended fiber fabric against Escherichia coli, Staphylococcus aureus, and Candida albicans were still greater than 70%, 80%, and 60%, respectively, meeting the requirements of 3A-level antibacterial textiles. Therefore, the polyester-cotton blended fiber fabric prepared in this example has excellent antibacterial performance, good biocompatibility, and long-term durability.

[0056] The copper-based antibacterial fibers prepared in Example 1 can also be blended and woven with natural fibers or other synthetic fibers to make various different textiles, such as clothing, masks, shoes, socks, backpacks, towels, and other textile products, with very broad application prospects.

[0057] Figure 3 This is a photo of the plate colony count in the antibacterial test of the polyester-cotton blended fiber fabric in Example 1. In the figure, E-B and S-B represent the blank control groups of Escherichia coli and Staphylococcus aureus respectively, and E-F3 and S-F3 represent the test groups of the polyester-cotton blended fiber fabric against Escherichia coli and Staphylococcus aureus respectively. It can be seen from Figure 3 that after the antibacterial fabric was co-cultured by oscillation, the number of colonies decreased significantly, indicating that the polyester-cotton blended fiber fabric has a strong antibacterial effect.

[0058] Figure 4 This is a morphological photo of L929 mouse fibroblasts in the cytotoxicity test of the polyester-cotton blended fiber fabric in Example 1. In the figure, L929-B and L929-F3 represent the negative control group and the test group of the polyester-cotton blended fiber fabric respectively. It can be seen from Figure 4 that in the negative control group, the cells were spindle-shaped, with strong refraction, and the cell processes were fully extended, and the morphology was normal. In the test group of the polyester-cotton blended fiber fabric, the cell morphology was normal, spindle-shaped or irregular triangular, and there was no obvious difference in the cell number and morphology compared with the negative control group, indicating a high cell survival rate and no cytotoxicity of the polyester-cotton blended fiber fabric.

[0059] Example 2

[0060] Step 1 is the same as Step 1 in Example 1.

[0061] Step 2: Mix the above antibacterial PET powder with PET powder evenly at an addition amount of 1 wt% (that is, the mass of the antibacterial PET powder accounts for 1 wt% of the total mass), control the moisture content to be less than 100 ppm, and melt-spin at 280 °C to make copper-based antibacterial fibers. The content of Cu / Cu2O composite microspheres in the copper-based antibacterial fibers is 2 wt‰, and the Cu / Cu2O composite microspheres are evenly dispersed in the copper-based antibacterial fibers.

[0062] The copper-based antibacterial fibers prepared in step 2 of Example 2 and cotton fibers were blended at a ratio of 65:35 to weave a polyester-cotton cloth mixed fiber fabric. According to Appendix B of "GB / T 21510-2008 Test Method for Antibacterial Properties of Nano-inorganic Materials", the antibacterial rates of this polyester-cotton cloth mixed fiber fabric against Escherichia coli and Staphylococcus aureus were >90%, and the antibacterial rate against Candida albicans was >80%; at the same time, according to "GB / T 16886.5-2017 In Vitro Cytotoxicity Test", the cell survival rate of L929 mouse fibroblasts measured for this polyester-cotton cloth mixed fiber fabric was 85.686%, and it could be determined as a non-cytotoxic product according to the five-level cytotoxicity classification. According to the requirements and specifications of "FZ / T 73023-2006 Antibacterial Knitted Fabrics", after washing 50 times, the antibacterial rates of this polyester-cotton cloth mixed fiber fabric against Escherichia coli and Staphylococcus aureus still reached 79.4% and 86.7%, meeting the requirements of 3A-level antibacterial textiles.

[0063] Example 3

[0064] Step 1: Add 50 L of ethylene glycol solution into a 100-L glass reactor. While stirring, add 2.5 kg of PVP powder with a molecular weight of 360,000. After it is completely dissolved, add 8 kg of PA6 powder and stir for 12 h. Then add 5155 g of CuCl2·H2O. After stirring until completely dissolved, slowly add 12.25 L of NaOH solution with a concentration of 12 mol / L. Then add 4 kg of anhydrous glucose and react for 15 min at 70 °C; finally, obtain antibacterial PA6 powder (antibacterial polymer powder) loaded with 20 wt% Cu / Cu2O composite microspheres. The average particle size of the Cu / Cu2O composite microspheres is about 600 nm.

[0065] Step 2: Mix the above antibacterial PA6 powder evenly with pure PA6 powder at an addition amount of 1.5 wt% (that is, the antibacterial PA6 powder accounts for 1.5 wt% of the total mass), control the moisture content to be less than 100 ppm, and melt-spin at 280 °C to make copper-based antibacterial fibers. The content of Cu / Cu2O composite microspheres in the copper-based antibacterial fibers is 3 wt‰, and the Cu / Cu2O composite microspheres are evenly dispersed in the copper-based antibacterial fibers.

[0066] Weave the copper-based antibacterial fibers prepared in step 2 of Example 3 into a knotted fishing net, and take a 10*10 cm 2 net piece and soak it in 1 L of simulated seawater. After soaking for one week, measure the concentration of Cu 2+ in the seawater to be 0.3 ppm, while the Cu 2+When the concentration is above 5 ppm, comparatively speaking, the copper-based antibacterial fiber prepared by the melt spinning method of the present invention is more long-lasting, durable, safe and stable. According to Appendix B of "GB / T 21510-2008 Test Method for Antibacterial Properties of Nano-inorganic Materials", the antibacterial rates of this knotted fishing net against Escherichia coli, Staphylococcus aureus and Candida albicans are all >99%. At the same time, according to "GB / T 16886.5-2017 In Vitro Cytotoxicity Test", the cell survival rate of L929 mouse fibroblasts measured for this knotted fishing net is 78.647%, and it can be determined as a non-cytotoxic product according to the five-level cytotoxicity classification. It has been proven by experiments that the knotted fishing net prepared by the present invention has excellent antibacterial properties and is long-lasting and durable, effectively inhibiting the attachment of marine fouling organisms on the surface of the fishing net, improving the service life of the fishing net, and having important practical significance.

[0067] The copper-based antibacterial fiber prepared in Example 3 woven into a net can also be applied to fields such as sunshade nets, seawater tank nets, air conditioner filters, and kitchen filters.

[0068] The above-described embodiments are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. An antibacterial polymer powder, characterized in that, It is a core-shell structure; the antibacterial polymer powder has a polymer as the core and a copper-based microsphere antibacterial agent as the shell; the loading amount of the copper-based microsphere antibacterial agent in the antibacterial polymer powder is 20 wt%. The copper-based microsphere antibacterial agent is a composite microsphere structure of Cu nanocrystals and Cu2O nanocrystals, with an average particle size of 100 - 600 nm. The polymer is at least one of polyethylene terephthalate, polyamide, polyethylene, polyurethane, polypropylene, and polyvinyl chloride. The preparation method of the antibacterial polymer powder includes the following steps: Polyvinylpyrrolidone and the polymer are successively added to an ethylene glycol solution, and then a divalent copper salt, an alkali solution, and glucose are successively added, followed by reaction to obtain the antibacterial polymer powder. The divalent copper salt is at least one of copper dichloride dihydrate, copper sulfate, copper nitrate, and copper acetate; the alkali solution is a NaOH solution with a concentration of 12 mol / L. The temperature of the reaction is 55 - 80 °C, and the time is 10 - 20 min. The volume-mass ratio of ethylene glycol, polyvinylpyrrolidone, polymer, divalent copper salt, alkali solution, and glucose is 50 L:2.5 kg:2 - 8 kg:1 - 6 kg:3 - 13 L:0.3 - 4 kg.

2. Use of the antibacterial polymer powder according to claim 1 in the preparation of antibacterial fibers.

3. A copper-based antibacterial fiber, characterized in that, Using the antibacterial polymer powder described in claim 1 as the effective antibacterial component of the fiber.

4. A method for preparing the copper-based antibacterial fiber according to claim 3, characterized in that, Including the following steps: The antibacterial polymer powder described in claim 1 is mixed evenly with the polymer and then melt-spun to obtain the copper-based antibacterial fiber.

5. According to the method for preparing the copper-based antibacterial fiber according to claim 4, characterized in that, By mass percentage, the addition amount of the antibacterial polymer powder is 0.5 wt% - 5 wt%; the content of the copper-based microsphere antibacterial agent in the copper-based antibacterial fiber is 0.1 wt% - 1 wt%.

6. Use of the copper-based antibacterial fiber according to claim 3 in the preparation of household textiles, medical gauze, military training uniforms or fishing nets.

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