A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber and its preparation method

Abstract

The present invention relates to a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber and a preparation method thereof. The product mainly consists of a PA6 matrix and self-assembled micro-nano structured Cu2O particles dispersed therein. The self-assembled micro-nano structured Cu2O is a micron-sized sphere formed by assembling multiple nano-sized Cu2O particles through physical and / or chemical forces between dendritic polymers. The preparation method is as follows: PA6 chips are melt-blended and spun with a high-concentration PA6 / micro-nano structured Cu2O masterbatch. In the Cu2O / PA6 antibacterial fiber of the present invention, Cu2O has good dispersion performance. When the fiber is stored in an indoor environment with a temperature of 25 °C and a relative humidity of 40% - 80%, Cu2O maintains its chemical stability without affecting the chromaticity and mechanical properties of the fiber. The fiber has antibacterial effects on Escherichia coli, Staphylococcus aureus, and Candida albicans. The method of the present invention is simple and is conducive to large-scale industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional fibers, and relates to a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber and a preparation method thereof. Background Art

[0002] Pathogenic bacteria exist in all aspects of people's lives, such as Staphylococcus aureus, Escherichia coli, Candida albicans. More seriously, the emergence of some drug-resistant bacteria poses a greater threat to human life safety. During the use of textiles, it is inevitable to be contaminated with pathogenic bacteria. Since ordinary fiber fabrics do not have bactericidal properties, they will become bases for the survival and reproduction of various germs. Nylon 6 (PA6), as a versatile fiber with wide applications, is widely used in the textile field due to its excellent abrasion resistance, fatigue resistance, and elastic recovery rate. However, PA6 is very prone to generating static electricity and thus attracting dust. Coupled with the sweat and oil excreted by the human body, it is very easy for bacteria and other microorganisms to grow on PA6 fibers. At the same time, people's requirements for fibers have gradually shifted from initial comfort and warmth to multifunctionality, especially the demand for antibacterial functions. Therefore, in order to achieve the antibacterial functionalization of PA6 fabrics, the development of antibacterial PA6 fibers becomes very meaningful.

[0003] Currently, in the antibacterial modification processing methods of PA6 fibers, the melt blending modification method is mainly adopted. Among them, the masterbatch method is the simplest and most convenient method for preparing PA6 antibacterial fibers by preparing an antibacterial masterbatch with a high antibacterial agent content and then blending and spinning the antibacterial masterbatch with PA6 chips. However, the current development of this method is not yet mature, and there are still problems such as the non-persistent antibacterial agent effect and poor heat resistance. Ying Ying et al. (Synthetic Fiber, 2009, 38(2): 26-29.) blended a silver-loaded nano-zinc oxide antibacterial agent with PA6 chips to obtain an antibacterial PA6 masterbatch, and then prepared antibacterial PA6 fibers with different antibacterial agent contents through melt blending and spinning. The results showed that when the addition amount was 1wt%, the bactericidal rates against Escherichia coli and Staphylococcus aureus were both above 97%. Aysin Dural Erem et al. (Carbohydrate Polymers, 2018, 200: 173-182.) used the melt spinning method to add nano-silver with a particle size less than 100nm into the PA6 matrix to make PA6 antibacterial composite fibers. When the addition amount reached 5wt%, the antibacterial rates against Klebsiella pneumoniae and Staphylococcus aureus were 53% and 99% respectively. However, in these studies, with the increase in the addition amount of the inorganic antibacterial agent, serious agglomeration of nanoparticles occurred in the fiber matrix, resulting in a decrease in the mechanical properties of the fibers.

[0004] Cu2O is an excellent semiconductor material with wide applications in antibacterial aspects. Generally, nano-scale Cu2O is extremely easy to be oxidized into CuO under high temperature or oxygen-rich conditions. Therefore, there are problems of poor chemical stability, easy agglomeration, and difficult dispersion during the application process. This results in that after the PA6 / Cu2O fibers prepared from Cu2O nanoparticles are used for a period of time, the color of the fibers will change significantly and the antibacterial performance will be greatly reduced, proving the instability of Cu2O in PA fibers. Therefore, the research on the preparation of PA6 / Cu2O antibacterial masterbatch is almost blank, and there is no relevant report on the spinning research of PA6 / Cu2O antibacterial masterbatch either. In recent years, researchers have found that constructing micro-nano structures can reduce the agglomeration degree of nano materials, making them have both the advantages of nano materials and integrating the good stability and easy separation characteristics of micro or sub-micro materials. Therefore, this patent aims to construct micro-nano structured Cu2O and prepare PA6 / Cu2O composite fibers, ultimately solving the dispersion and stability problems of Cu2O in PA fibers and maintaining the mechanical properties of the fibers. Summary of the Invention

[0005] The object of the present invention is to provide a Cu2O / PA6 fiber to solve the problems of non-persistent antibacterial effect and poor heat resistance existing in the existing PA6 antibacterial fibers. By constructing micro-nano structured Cu2O and preparing PA6 / Cu2O composite fibers, the dispersion, stability, and antibacterial performance of Cu2O in PA fibers are improved, and the mechanical properties of the fibers are maintained.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber mainly consists of a PA6 matrix and self-assembled micro-nano structured Cu2O particles dispersed therein;

[0008] The self-assembled micro-nano structured Cu2O particles are micron-scale spheres formed by assembling multiple nano-scale Cu2O particles. Among them, the assembly utilizes the physical and / or chemical forces between dendritic polymers;

[0009] The structural formula of the dendritic polymer is as follows:

[0010]

[0011] In the formula, the wavy line represents a dendritic polymer that can further react to form more branched units;

[0012] The chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber at the end of just spinning is 66.62 - 66.80, the a value is 0.29 - 0.32, and the b value is 13.3 - 14.3. After being placed in an indoor environment at 25°C and a relative humidity of 40% - 80% for one year, the change rates of the chromaticity L value, a value, and b value are all less than 4%.

[0013] The antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber against Escherichia coli is >99.99% at the end of just spinning, the antibacterial rate against Staphylococcus aureus is >99.99%, and the antibacterial rate against Candida albicans is ≥50%. After being placed in an indoor environment at 25°C and a relative humidity of 40% - 80% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are all less than 2%.

[0014] One of the technical problems to be solved by the present invention is that in the prior art, after the PA6 / Cu2O fiber prepared from Cu2O nanoparticles is used for a period of time, the color of the fiber will change significantly and the antibacterial performance will be greatly reduced. This is because the Cu2O nanoparticles are unstable in the PA fiber. The reason is that the commercially available Cu2O nanoparticles are very easy to agglomerate, forming micron-sized particles, and the final size becomes a mixed state of micron-sized and nano-sized, as Figure 1 shown; the reason why the present invention can solve this technical problem existing in the prior art is that the self-assembled micro-nano structured Cu2O particles of the present invention always maintain a uniform micron structure in large sizes and always maintain a uniform nano-particle accumulation in small sizes, as Figure 2 shown.

[0015] Another technical problem to be solved by the present invention is that the antibacterial performance of the commercially available Cu2O nanoparticles needs to be further improved. Although the commercially available Cu2O nanoparticles have smaller particle sizes, the self-assembled micro-nano structured Cu2O particles of the present invention are composed of primary particles of several nanometers and there is no agglomeration phenomenon, which makes the self-assembled micro-nano structured Cu2O particles of the present invention have a larger specific surface area than the commercially available Cu2O nanoparticles, thus endowing the micro-nano structured Cu2O with excellent antibacterial performance.

[0016] As a preferred technical solution:

[0017] A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, wherein the content of the self-assembled micro-nano structured Cu2O particles in the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 0.4 - 1.2 wt%; the denier of the single filament of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 5.6 - 8.0 dtex, and the breaking strength is 4.0 - 5.5 cN / dtex; the antibacterial rate of the self-assembled micro-nano structured Cu2O particles against Escherichia coli is above 99.999%, the antibacterial rate against Staphylococcus aureus is above 99.999%, the antibacterial rate against Candida albicans is above 97.29%, the antibacterial rate against methicillin-resistant Staphylococcus aureus is above 99.999%, and the antibacterial rate against vancomycin-resistant Enterococcus is above 99.999%.

[0018] A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, wherein the average particle size of the nano-scale Cu2O particles is 8 - 10 nm, and the average particle size of the micro-scale spheres is 1.0 - 1.6 μm.

[0019] A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, wherein the degree of branching DB of the dendritic polymer is 0.45 - 0.55, and the number-average molecular weight Mn is 45000 - 60000 g / mol.

[0020] A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, wherein the specific surface area of the self-assembled micro-nano structured Cu2O particles is 30 - 60 m 2 ·g -1 , and the content of the dendritic polymer in the self-assembled micro-nano structured Cu2O particles is 23.2 - 24.2 wt%.

[0021] The present invention also provides a method for preparing a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber, which is prepared by melt-blending and spinning PA6 chips with a high-concentration PA6 / micro-nano structured Cu2O masterbatch to obtain a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber;

[0022] The content of the self-assembled micro-nano structured Cu2O particles in the high-concentration PA6 / micro-nano structured Cu2O masterbatch is 10 - 20 wt%;

[0023] The preparation process of the self-assembled micro-nano structured Cu2O particles is as follows: First, a dendritic polymer is synthesized by the A2 + B3 method using benzene-1,2,3-tricarboxylic acid and 1,2-ethanedithiol as raw materials. Then, the dendritic polymer is added to an aqueous solution of polyetheramine to form a homogeneous and transparent reaction system. Next, a copper salt solution is dropped into the reaction system under stirring and stirring is continued for a period of time. Finally, an aqueous solution of ascorbic acid is dropped into the reaction system under stirring and stirring is continued for a period of time to obtain self-assembled micro-nano structured Cu2O particles.

[0024] As a preferred technical solution:

[0025] For the preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, the mass ratio of PA6 chips to the high-concentration PA6 / micro-nano structured Cu2O masterbatch is 5-10:1; before melt-blending spinning, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are dried. The drying process is as follows: first, vacuum dry at 80°C for 10 h to remove most of the moisture, and then vacuum dry at 130°C for 24 h to remove the crystal water; the process parameters of melt-blending spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 255-265°C, temperature of the second zone of the screw 270-275°C, temperature of the third zone of the screw 265-268°C, temperature of the fourth zone of the screw 265-268°C, temperature of the GP2 box 265-268°C, temperature of the PP2 box 265-268°C, temperature of the SP box 264-268°C, temperature of the hot roller 65-68°C, heat setting temperature 130-135°C.

[0026] For the preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, the preparation process of the high-concentration PA6 / micro-nano structured Cu2O masterbatch is as follows: first, premix PA6 powder or chips (the effect of the powder is better, and if the chips are too large in size, there may be uneven mixing. The average particle size of the powder is preferably 120±30 μm) and self-assembled micro-nano structured Cu2O particles. The content of the self-assembled micro-nano structured Cu2O particles in the premixed product is 10-20 wt%, and then the premixed product is melt-blended and extruded into pellets to obtain the high-concentration PA6 / micro-nano structured Cu2O masterbatch.

[0027] For the preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, before premixing, the PA6 powder or chips and the self-assembled micro-nano structured Cu2O particles are dried. The drying temperature is 120-130°C and the time is 12-15 h; the premixing is carried out using a stainless steel crusher, and the premixing time is 45-60 min; the melt-blending is carried out using a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder are 235°C, 253°C, 253°C, 253°C, 253°C respectively, the temperature of the die head is 255-265°C, and the screw speed is 160-180 rpm.

[0028] For the preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, the preparation steps of the self-assembled micro-nano structured Cu2O particles are as follows:

[0029] (1) Synthesize dendritic polymers;

[0030] First, mix the benzene tricarboxylic acid, 1,2-ethanedithiol and H2O in a ratio of 0.1 - 0.2 mol: 0.1 - 0.15 mol: 100 mL, then heat the mixture to 120 - 150 °C and keep it warm for a period of time until more than 80% of the H2O is distilled off. Then evacuate to 0.098 MPa while heating to 145 - 165 °C, and keep the temperature and pressure constant for reaction for 2 - 2.5 h to obtain a dendritic polymer;

[0031] (2) Prepare an aqueous solution of polyetheramine;

[0032] Add polyetheramine to deionized water, and stir magnetically at a temperature of 20 - 30 °C to fully dissolve and form an aqueous solution of polyetheramine;

[0033] (3) Keep the stirring speed and temperature unchanged, and add the dendritic polymer to the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system;

[0034] (4) Under stirring conditions, add the copper salt solution dropwise to the reaction system through a constant-pressure dropping funnel, and then continue stirring for 1 h;

[0035] (5) Under stirring conditions, add the aqueous solution of ascorbic acid dropwise to the reaction system through a constant-pressure dropping funnel, and then continue stirring for 2 - 3 h;

[0036] (6) Post-treatment;

[0037] Filter by suction, wash and dry to obtain self-assembled micro-nano structured Cu2O particles.

[0038] In the preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber as described above, in step (2), the polyetheramine is polyetheramine M-600; the mass ratio of polyetheramine to deionized water is 1:4 - 6; the stirring speed is 300 - 400 r / min;

[0039] In step (3), the mass ratio of the dendritic polymer to polyetheramine is 1:15 - 20;

[0040] In step (4), the stirring speed is 300 - 400 r / min; the concentration of the copper salt solution is 0.15 - 0.175 M and is composed of copper acetate monohydrate and deionized water; the dropping rate is 3 - 4 drops / second; the mass ratio of the copper salt solution to the dendritic polymer is 1:2 - 3;

[0041] In step (5), the stirring speed is 300 - 400 r / min; the concentration of the aqueous solution of ascorbic acid is 0.7 - 0.875 M; the molar ratio of ascorbic acid to copper ions in the reaction system is 1:2; the dropping rate is 3 - 4 drops / second.

[0042] Beneficial effects:

[0043] (1) A self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber of the present invention can achieve uniform and stable dispersion of micro-nano structured Cu₂O nanoparticles in PA6 fibers, enabling Cu₂O to maintain a micron-scale dispersion in PA6 while exerting the antibacterial effect of nano-scale particles, so that the prepared Cu₂O / PA6 antibacterial fiber has stable, long-lasting, and persistent antibacterial properties. In addition, Cu₂O in this product can maintain long-term chemical stability in the PA6 fiber matrix (i.e., no chemical oxidation or chemical reduction reaction occurs), and macroscopically, it shows that there is no obvious color change after the Cu₂O / PA6 antibacterial fiber is spun and placed in an indoor environment at 25 °C and a relative humidity of 40% - 80% for one year.

[0044] (2) A preparation method of a self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber of the present invention fixes a surfactant on the surface of the micro-nano structured Cu₂O, increasing the binding force between Cu₂O and the PA6 matrix and improving the concentration and dispersion stability of Cu₂O in PA6. The method of preparing antibacterial fibers by melt spinning is simple and efficient, suitable for large-scale industrial production, and provides the possibility for the industrialization and marketization of self-assembled micro-nano structured Cu₂O / PA6 antibacterial fibers. Description of the Drawings

[0045] Figure 1 SEM image of commercially available cuprous oxide powder with a particle size of 100 nm;

[0046] Figure 2 SEM images of the micro-nano structured Cu₂O prepared by the present invention at different magnifications;

[0047] Figure 3 Fiber diagrams prepared in Examples 1 - 3 and Comparative Example 1;

[0048] Figure 4 Optical microscope diagrams of the cross-sections of the antibacterial fibers prepared in Examples 1 - 3; among them, (a1) is pure PA at low magnification, (a2) is pure PA at high magnification, (b1) is PA / 0.4 wt% Cu₂O at low magnification, (b2) is PA / 0.4 wt% Cu₂O at high magnification, (c1) is PA / 0.8 wt% Cu₂O at low magnification, (c2) is PA / 0.8 wt% Cu₂O at high magnification, (d1) is PA / 1.2 wt% Cu₂O at low magnification, and (d2) is PA / 1.2 wt% Cu₂O at high magnification;

[0049] Figure 5 Antibacterial plate diagrams of the antibacterial fibers prepared in Examples 1 - 3 and Comparative Example 1 and the blank sample;

[0050] Figure 6Antibacterial plate diagrams of commercially available cuprous oxide powder with a particle size of 100 nm and the self-assembled micro-nano structured Cu2O prepared in Example 1. Detailed implementation manners

[0051] The present invention will be further described below in conjunction with the detailed implementation manners. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0052] In the examples, a two-component composite spinning machine of model Ф25×2 of Japanese Abe Company was used for spinning experiments;

[0053] In the fiber examples and comparative examples, the antibacterial properties of the PA6 / Cu2O composite fibers were tested by the oscillation method according to GB / T 20944.3-2008. The specific process is as follows: First, wash the oil agent on the fiber surface with absolute ethanol, and then dry the surface ethanol and cut it into pieces. Weigh 750 mg of the fiber sample and sterilize it in an autoclave at 121 °C for 30 min for standby. Oscillate and culture Escherichia coli and Staphylococcus aureus in a suitable nutrient broth culture medium at 37 °C for 18 h, and oscillate and culture Candida albicans in a suitable nutrient broth culture medium at 28 °C for 24 h. Disperse 7.5 mg of the cut PA6 / Cu2O composite fiber in 100 mL of a nutrient solution containing about 10 4 ~10 6 CFU / mL of Escherichia coli, Staphylococcus aureus or Candida albicans, and after oscillating and culturing at 37 °C (28 °C for Candida albicans) for 18 h, take out 1.0 ± 0.1 mL of the bacterial suspension from the test bottle, and dilute it to a certain amount by a 10-fold dilution method to ensure that the colonies cultured can be easily and correctly counted. The diluted solution is evenly spotted on the broth agar plate, with three parallel controls for each concentration, and incubated at 37 °C for 18 h (cultured at 28 °C for 48 h for Candida albicans). Take pictures and calculate the number of colony-forming units (CFU) of bacteria on each plate, and calculate the antibacterial rate of the material through the following formula:

[0054]

[0055] Among them, R is the antibacterial rate of the material; CFUctrl is the average number of colonies after the control group contacts the test bacteria for 18 h; CFUexpt is the average number of colonies after the experimental group contacts the test bacteria for 18 h.

[0056] In the examples and comparative examples of Cu2O powder, the test methods for the antibacterial properties of powder broth agar plates (i.e., blank samples), commercially available micron-scale and nano-scale mixed Cu2O, and micro-nano structured Cu2O are as follows: The oscillating method is used to quantitatively test the antibacterial properties of commercially available micron-scale and nano-scale mixed Cu2O and micro-nano structured Cu2O according to GB / T 20944.3-2008. At 37 °C and 200 rpm in a shaker, the strains are incubated in a suitable culture medium (Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus grow in LB broth; Enterococcus faecium resistant to vancomycin grows in BHI medium; Candida albicans grows in YM medium) until the logarithmic phase, and then washed 3 times with PBS to obtain a pre-prepared bacterial suspension. The Cu2O sample is dispersed in PBS to prepare an appropriate 256 mg / L sample solution, and 100 μL of the sample solution and 100 μL of the bacterial suspension are added to a 96-well plate respectively, and then incubated for 12 h. After incubation, the bacterial suspension is serially diluted 10-fold with sterile PBS and spotted on a plate containing the corresponding culture medium, and incubated at an appropriate temperature for a certain time (Candida albicans is incubated at 28 °C for 48 h, and other strains are incubated at 37 °C for 18 h), and each group of experiments is parallel-controlled three times to ensure the repeatability of the experiment. Calculate the number of colony-forming units (CFU) of bacteria on each plate, and calculate the antibacterial rate of the material through the following formula:

[0057]

[0058] Where R is the antibacterial rate of the material; CFU ctrl is the average number of colonies after the control group contacts the test bacteria for 12 h; CFU expt is the average number of colonies after the experimental group contacts the test bacteria for 12 h.

[0059] PA6 in the specific implementation manner is produced by Suzhou Baolidi Material Co., Ltd., industrial grade; the commercially available 100 nm Cu2O powder is produced by Beijing Decod Island Gold Technology Co., Ltd., with a purity of 99%.

[0060] Example 1

[0061] A preparation method of self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber, the specific steps are as follows:

[0062] (1) Preparation of self-assembled micro-nano structured Cu2O particles;

[0063] (1.1) Synthesis of dendritic polymers;

[0064] First, benzene-1,2,3-tricarboxylic acid, 1,2-ethanedithiol and H2O were mixed in a ratio of 0.1 mol: 0.1 mol: 100 mL, and then the temperature was raised to 120 °C and held for a period of time until 80% of the H2O was distilled off. Then, the vacuum was pumped to 0.098 MPa while the temperature was raised to 145 °C, and the reaction was carried out under constant temperature and pressure for 2.5 h to obtain a dendritic polymer.

[0065] The degree of branching DB of the obtained dendritic polymer was 0.45, and the number-average molecular weight Mn was 45000 g / mol; the structural formula of the dendritic polymer was: In the formula, the wavy line represents a dendritic polymer that can further react to form more branched units;

[0066] (1.2) Prepare an aqueous solution of polyetheramine;

[0067] According to a mass ratio of 1:4, polyetheramine M-600 was added to deionized water, and under the temperature condition of 20 °C, magnetic stirring was carried out at a stirring speed of 400 r / min to fully dissolve and form an aqueous solution of polyetheramine.

[0068] (1.3) Keeping the stirring speed and temperature unchanged, the dendritic polymer prepared in step (1.1) was added to the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system; among them, the mass ratio of the dendritic polymer to polyetheramine was 1:15.

[0069] (1.4) Under the stirring condition of a stirring speed of 400 r / min, a copper salt solution composed of copper acetate monohydrate and deionized water with a concentration of 0.15 M was added dropwise to the reaction system through a constant-pressure dropping funnel at a dropping rate of 3 drops / second, and then stirring was continued for 1 h; the mass ratio of the copper salt solution to the dendritic polymer was 1:2.

[0070] (1.5) Under the stirring condition of a stirring speed of 300 r / min, an aqueous solution of ascorbic acid with a concentration of 0.7 M was added dropwise to the reaction system through a constant-pressure dropping funnel at a dropping rate of 3 drops / second, and then stirring was continued for 2 h; the molar ratio of ascorbic acid to copper ions in the reaction system was 1:2.

[0071] (1.6) Post-treatment;

[0072] Filter by suction, wash and dry to obtain self-assembled micro-nano structured Cu2O particles;

[0073] The self-assembled micro-nano structured Cu2O particles are micron-scale spheres assembled from multiple nano-scale Cu2O particles; among them, the assembly utilizes physical and / or chemical forces between dendritic polymers; the specific surface area of the self-assembled micro-nano structured Cu2O particles is 30 m 2 ·g -1; The average particle size of the nanoscale Cu2O particles is 8 nm, and the average particle size of the microscale spheres is 1 μm;

[0074] (2) Preparation of high-concentration PA6 / micro-nano structured Cu2O masterbatch;

[0075] First, the PA6 powder and the self-assembled micro-nano structured Cu2O particles are dried at 120 °C for 15 h, then premixed using a stainless-steel crusher for 45 min. The content of the self-assembled micro-nano structured Cu2O particles in the premixed product is 10 wt%. Finally, the premixed product is melt-blended and pelletized to obtain the high-concentration PA6 / micro-nano structured Cu2O masterbatch; among them, the melt-blending is carried out using a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder are 235 °C, 253 °C, 253 °C, 253 °C, 253 °C respectively, the head temperature is 255 °C, and the screw speed is 160 rpm;

[0076] (3) Preparation of self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0077] First, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are vacuum-dried at 80 °C for 10 h, then vacuum-dried at 130 °C for 24 h. Finally, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are melt-blended and spun to obtain the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0078] Among them, the process parameters of the melt-blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 255 °C, temperature of the second zone of the screw 270 °C, temperature of the third zone of the screw 265 °C, temperature of the fourth zone of the screw 265 °C, temperature of the GP2 box 265 °C, temperature of the PP2 box 265 °C, temperature of the SP box 264 °C, temperature of the hot roller 65 °C, heat setting temperature 130 °C.

[0079] The finally prepared self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber is composed of a PA6 matrix and self-assembled micro-nano structured Cu₂O particles with a content of 0.4 wt% dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber at the end of spinning is 66.62, the a value is 0.29, and the b value is 13.3. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the chromaticity L value, a value, and b value are 3.4%, 2.7%, and 3.8% respectively; the antibacterial rate of the self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber against Escherichia coli at the end of spinning is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 50%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 1%, 0.8%, and 1.1% respectively; the single filament fineness of the self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber is 5.6 dtex, and the breaking strength is 4 cN / dtex.

[0080] Comparative Example 1

[0081] A preparation method of PA6 fiber, the raw material is the same PA6 chips as in Example 1, and the preparation method is the melt spinning method, and the process parameters are the same as in Example 1.

[0082] The chromaticity L value of the finally prepared PA6 fiber at the end of spinning is 92, the a value is -4, and the b value is 19. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the chromaticity L value, a value, and b value are 0.2%, 0.2%, and 0.3% respectively; the antibacterial rate against Escherichia coli at the end of spinning is 9.68%, the antibacterial rate against Staphylococcus aureus is 14.71%, and the antibacterial rate against Candida albicans is 0%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 1%, 1%, and 2% respectively; the single filament fineness is the same as in Example 1, and the breaking strength is 4.6 cN / dtex.

[0083] Example 2

[0084] A preparation method of self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber is basically the same as in Example 1, the only difference is that the added content of the high-concentration PA6 / micro-nano structured Cu₂O masterbatch is different, so that the content of the self-assembled micro-nano structured Cu₂O particles in the self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber is 0.8 wt%.

[0085] The finally prepared self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is composed of a PA6 matrix and self-assembled micro-nano structured Cu2O particles dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber at the end of spinning is 66.70, the a value is 0.29, and the b value is 13.7. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the chromaticity L value, a value, and b value are 3.2%, 2.7%, and 2.9% respectively; the antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber against Escherichia coli at the end of spinning is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 60.53%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 1.2%, 1.8%, and 1.5% respectively; the single filament fineness of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 5.6 dtex, and the breaking strength is 5.0 cN / dtex.

[0086] Example 3

[0087] A preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is basically the same as that of Example 1, except that the added content of the high-concentration PA6 / micro-nano structured Cu2O masterbatch is different, so that the content of the self-assembled micro-nano structured Cu2O particles in the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 1.2 wt%.

[0088] The finally prepared self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is composed of a PA6 matrix and self-assembled micro-nano structured Cu2O particles dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber at the end of spinning is 66.8, the a value is 0.30, and the b value is 14.0. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the chromaticity L value, a value, and b value are 3.1%, 2.9%, and 2.2% respectively; the antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber against Escherichia coli at the end of spinning is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 76.32%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 60% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 0.9%, 1.2%, and 1.6% respectively; the single filament fineness of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 7.5 dtex, and the breaking strength is 5.5 cN / dtex.

[0089] As Figure 3As shown, the fibers prepared in Example 1, Example 2, Example 3 and Comparative Example 1 are respectively. In Example 1, Example 2, Example 3 and Comparative Example 1, according to the evaluation of the antibacterial properties of textiles in GBT 20944.3-2008, when the antibacterial rate of the sample against Escherichia coli and Staphylococcus aureus is ≥70%, or the antibacterial rate against Candida albicans is ≥60%, it is considered that the sample has antibacterial effect.

[0090] As Figure 5 shown, the antibacterial test results show that taking the blank medium without adding any materials as the comparative sample, the antibacterial rates of pure PA6 fiber against Escherichia coli, Staphylococcus aureus and Candida albicans are 9.68%, 14.71% and 0% respectively, and it does not have obvious antibacterial effect. When self-assembled micro-nano structured Cu2O is added, the antibacterial effect of PA6 / Cu2O composite fiber is significantly enhanced, and the antibacterial effect is better with the increase of the addition amount of micro-nano structured Cu2O.

[0091] As Figure 4 shown, during the spinning process, there is no obvious agglomeration and uneven dispersion of micro-nano structured Cu2O, indicating that the micro-nano structured Cu2O coated with surface hyperbranched molecules increases the compatibility with the PA matrix, and the color stability also shows from the side that the micro-nano structure improves the stability of Cu2O in the matrix. It is precisely because of the improvement of compatibility and stability that the excellent broad-spectrum antibacterial properties of Cu2O / PA6 composite fiber are guaranteed.

[0092] Comparative Example 2

[0093] A preparation method of antibacterial fiber is basically the same as that of Example 1, the difference is only that in step (2), the added is not the self-assembled micro-nano structured Cu2O particles prepared in step (1), but the commercially available cuprous oxide powder with a particle size of 100 nm.

[0094] The finally prepared antibacterial fiber has a chromaticity L value of 73, an a value of 7, and a b value of 94 after just finishing spinning. After being placed in an indoor environment at a temperature of 25°C and a relative humidity of 60% for one year, the change rates of the chromaticity L value, a value, and b value are 24.6%, 71.4%, and 34.0% respectively; the antibacterial rate against Escherichia coli is 99.991% after just finishing spinning, the antibacterial rate against Staphylococcus aureus is 99.991%, and the antibacterial rate against Candida albicans is 36%. After being placed in an indoor environment at a temperature of 25°C and a relative humidity of 60% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 5.0%, 5.5%, and 11% respectively; the denier per filament of the antibacterial fiber is 5.7 dtex, and the breaking strength is 3.3 cN / dtex.

[0095] Comparing Comparative Example 2 with Example 1, the antibacterial property right after spinning is lower than that of the composite fiber in Example 1. After the fibers in Comparative Example 2 are placed for one year under the same conditions as the fibers in Example 1, their antibacterial stability and chemical stability (change in fiber color) deteriorate significantly. Under similar denier conditions, the breaking strength of the composite fiber spun from commercially available Cu2O is significantly lower than that of the PA6 composite fiber with self-assembled micro-nano structured Cu2O. This is because commercially available Cu2O easily agglomerates during the spinning process, losing a certain specific surface area, resulting in an unsatisfactory antibacterial property of its fiber composite. In addition, excessive agglomeration causes stress concentration points in the fiber, thus reducing the breaking strength of the composite fiber. The effective hyperbranched polymer modification on the surface of self-assembled micro-nano structured Cu2O improves the interfacial compatibility between it and the PA6 matrix, and at the same time plays a certain role in chemically stabilizing and protecting Cu2O. Therefore, the fiber color changes little. The PA6 composite fiber spun from commercially available Cu2O undergoes a redox reaction due to commercially available Cu2O under environmental temperature and humidity, affecting the chromaticity of the fiber. In addition, the redox reaction changes the composition of Cu2O, which in turn reduces the antibacterial property of the composite fiber in Comparative Example 2.

[0096] In addition, the antibacterial properties of a blank broth agar plate, the self-assembled micro-nano structured Cu2O particles prepared in Example 1, and commercially available cuprous oxide powder with a particle size of 100 nm were compared, as Figure 6As shown, the antibacterial rates of the blank broth agar plate against Escherichia coli, Staphylococcus aureus, Candida albicans, methicillin-resistant Staphylococcus aureus, and vancomycin-resistant Enterococcus are all 0%; the antibacterial rates of the self-assembled micro-nano structured Cu₂O particles prepared in Example 1 against Escherichia coli, Staphylococcus aureus, Candida albicans, methicillin-resistant Staphylococcus aureus, and vancomycin-resistant Enterococcus are 99.999%, 99.999%, 97.29%, 99.999%, and 99.999% respectively; the antibacterial rates of the commercially available cuprous oxide powder with a particle size of 100 nm against Escherichia coli, Staphylococcus aureus, Candida albicans, methicillin-resistant Staphylococcus aureus, and vancomycin-resistant Enterococcus are 90.00%, 99.999%, 28.57%, 80.77%, and 99.97% respectively. Comparing the three, the self-assembled micro-nano structured Cu₂O has a higher antibacterial rate than the commercially available Cu₂O, especially for the bactericidal effect on Candida albicans, which has increased from 28.57% to 97.29%. The antibacterial rates of the self-assembled micro-nano structured Cu₂O against Escherichia coli and Staphylococcus aureus can both reach over 99.99%. For the two superbugs (methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus), it demonstrates the broad-spectrum antibacterial property of Cu₂O, showing a better antibacterial effect than the commercially available Cu₂O, with antibacterial rates all reaching over 99.99%. Although the commercially available 100 nm Cu₂O has a smaller particle size, it is very easy to agglomerate into larger micron-sized particles, while the large particles of the self-assembled micro-nano structured Cu₂O are composed of primary particles of several nanometers and there is no agglomeration phenomenon, which makes the self-assembled micro-nano structured Cu₂O have a larger specific surface area than the commercially available Cu₂O, thus endowing the micro-nano structured Cu₂O with excellent antibacterial effects.

[0097] Example 4

[0098] A preparation method of a self-assembled micro-nano structured Cu₂O / PA6 antibacterial fiber is as follows:

[0099] (1) Preparation of self-assembled micro-nano structured Cu₂O particles;

[0100] (1.1) Synthesis of dendritic polymers;

[0101] First, trimellitic acid, 1,2-ethanedithiol, and H₂O were mixed in a ratio of 0.12 mol:0.11 mol:100 mL, then heated to 125 °C and held for a period of time until 83% of the H₂O was distilled off, then evacuated to 0.098 MPa, and at the same time heated to 148 °C, and held under pressure for 2.4 h to obtain dendritic polymers;

[0102] The degree of branching DB of the prepared dendrimer is 0.52, and the number-average molecular weight Mn is 53,240 g / mol; the structural formula of the dendrimer is: In the formula, the wavy line represents a dendrimer that can further react to form more branched units;

[0103] (1.2) Prepare an aqueous solution of polyetheramine;

[0104] Add polyetheramine M-600 to deionized water according to a mass ratio of 1:5, and carry out magnetic stirring at a stirring speed of 390 r / min under the temperature condition of 22 °C to fully dissolve and form an aqueous solution of polyetheramine;

[0105] (1.3) Keeping the stirring speed and temperature unchanged, add the dendrimer prepared in step (1.1) to the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system; among them, the mass ratio of the dendrimer to polyetheramine is 1:16;

[0106] (1.4) Under the stirring condition of a stirring speed of 390 r / min, add a copper salt solution composed of copper acetate monohydrate and deionized water with a concentration of 0.155 M to the reaction system drop by drop through a constant pressure dropping funnel at a dropping rate of 3 drops / second, and then continue stirring for 1 h; the mass ratio of the copper salt solution to the dendrimer is 1:2;

[0107] (1.5) Under the stirring condition of a stirring speed of 320 r / min, add an aqueous solution of ascorbic acid with a concentration of 0.74 M to the reaction system drop by drop through a constant pressure dropping funnel at a dropping rate of 3 drops / second, and then continue stirring for 2 h; the molar ratio of ascorbic acid to copper ions in the reaction system is 1:2;

[0108] (1.6) Post-treatment;

[0109] Carry out suction filtration, washing and drying to obtain self-assembled micro-nano structured Cu2O particles;

[0110] The self-assembled micro-nano structured Cu2O particles are micron-sized spheres assembled from multiple nano-sized Cu2O particles; among them, the assembly utilizes the physical and / or chemical forces between dendrimers; the specific surface area of the self-assembled micro-nano structured Cu2O particles is 36 m 2 ·g -1 ; the average particle size of the nano-sized Cu2O particles is 8.6 nm, and the average particle size of the micron-sized spheres is 1.2 μm;

[0111] (2) Preparation of high-concentration PA6 / micro-nano structured Cu2O masterbatch;

[0112] The PA6 powder and self-assembled micro-nano structured Cu2O particles were first dried at 122 °C for 14 h, and then premixed using a stainless-steel pulverizer for 48 min. The content of self-assembled micro-nano structured Cu2O particles in the premixed product was 13 wt%. Finally, the premixed product was melt-blended and pelletized to obtain a high-concentration PA6 / micro-nano structured Cu2O masterbatch. Among them, the melt-blending was carried out using a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder were 235 °C, 253 °C, 253 °C, 253 °C, 253 °C respectively, the head temperature was 257 °C, and the screw speed was 163 rpm.

[0113] (3) Preparation of self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0114] First, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch were vacuum-dried at 80 °C for 10 h, then vacuum-dried at 130 °C for 24 h. Finally, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch were melt-blended and spun to obtain self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers.

[0115] Among them, the process parameters of the melt-blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 256 °C, temperature of the second zone of the screw 271 °C, temperature of the third zone of the screw 266 °C, temperature of the fourth zone of the screw 266 °C, temperature of the GP2 box 266 °C, temperature of the PP2 box 266 °C, temperature of the SP box 266 °C, temperature of the hot roll 66 °C, heat setting temperature 131 °C.

[0116] The finally obtained self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers are composed of a PA6 matrix and self-assembled micro-nano structured Cu2O particles with a content of 0.5 wt% dispersed therein. The chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers just after spinning is 66.63, the a value is 0.29, and the b value is 13.4. After being placed in an indoor environment at 25 °C and a relative humidity of 40% for one year, the change rates of the chromaticity L value, a value, and b value are 3.3%, 3.8%, and 2.4% respectively. The antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers against Escherichia coli is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 53.2%. After being placed in an indoor environment at 25 °C and a relative humidity of 40% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 0.98%, 1.1%, and 1.2% respectively. The denier per filament of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers is 6.2 dtex, and the breaking strength is 4.4 cN / dtex.

[0117] Example 5

[0118] A preparation method of self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers comprises the following specific steps:

[0119] (1) Preparation of self-assembled micro-nano structured Cu2O particles;

[0120] (1.1) Synthesis of dendritic polymer;

[0121] First, trimellitic acid, 1,2-ethanedithiol and H2O are mixed in a ratio of 0.14 mol: 0.12 mol: 100 mL, then the temperature is raised to 130 °C and kept for a period of time until 86% of H2O is distilled out. Then, the vacuum is pumped to 0.098 MPa while the temperature is raised to 152 °C, and the reaction is carried out under constant temperature and pressure for 2.3 h to obtain the dendritic polymer;

[0122] The degree of branching DB of the obtained dendritic polymer is 0.48, and the number-average molecular weight Mn is 48960 g / mol; the structural formula of the dendritic polymer is: In the formula, the wavy line represents the dendritic polymer that can further react to form more branched units;

[0123] (1.2) Preparation of polyetheramine aqueous solution;

[0124] According to the mass ratio of 1:6, polyetheramine M-600 is added to deionized water, and under the temperature condition of 24 °C, magnetic stirring is carried out at a stirring speed of 380 r / min to fully dissolve and form a polyetheramine aqueous solution;

[0125] (1.3) Keeping the stirring speed and temperature unchanged, the dendritic polymer prepared in step (1.1) is added to the polyetheramine aqueous solution to form a homogeneous and transparent reaction system; among them, the mass ratio of the dendritic polymer to polyetheramine is 1:17;

[0126] (1.4) Under the stirring condition of a stirring speed of 380 r / min, a copper salt solution composed of copper acetate monohydrate and deionized water with a concentration of 0.16 M is added dropwise to the reaction system through a constant pressure dropping funnel at a dropping rate of 3 drops / second, and then stirring is continued for 1 h; the mass ratio of the copper salt solution to the dendritic polymer is 1:2;

[0127] (1.5) Under the stirring condition of a stirring speed of 340 r / min, an aqueous solution of ascorbic acid with a concentration of 0.78 M is added dropwise to the reaction system through a constant pressure dropping funnel at a dropping rate of 3 drops / second, and then stirring is continued for 2 h; the molar ratio of ascorbic acid to copper ions in the reaction system is 1:2;

[0128] (1.6) Post-treatment;

[0129] By suction filtration, washing and drying, self-assembled micro-nano structured Cu₂O particles were obtained;

[0130] The self-assembled micro-nano structured Cu₂O particles are micron-sized spheres formed by the assembly of multiple nano-sized Cu₂O particles; among them, the assembly utilizes the physical and / or chemical forces between dendritic polymers; the specific surface area of the self-assembled micro-nano structured Cu₂O particles is 40 m 2 ·g -1 ⁻¹; the average particle size of the nano-sized Cu₂O particles is 9.2 nm, and the average particle size of the micron-sized spheres is 1.3 μm;

[0131] (2) Preparation of high-concentration PA6 / micro-nano structured Cu₂O masterbatch;

[0132] First, the PA6 powder and the self-assembled micro-nano structured Cu₂O particles were dried at 124 °C for 13 h, then the PA6 powder and the self-assembled micro-nano structured Cu₂O particles were premixed using a stainless-steel pulverizer, the premixing time was 52 min, and the content of the self-assembled micro-nano structured Cu₂O particles in the premixed product was 15 wt%, and finally the premixed product was melt-blended and extruded into pellets to obtain the high-concentration PA6 / micro-nano structured Cu₂O masterbatch; among them, the melt-blending was carried out using a twin-screw extruder, and the temperatures of the first to fifth zones of the twin-screw extruder were 235 °C, 253 °C, 253 °C, 253 °C, 253 °C respectively, the head temperature was 260 °C, and the screw speed was 166 rpm;

[0133] (3) Preparation of self-assembled micro-nano structured Cu₂O / PA6 antibacterial fibers;

[0134] First, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu₂O masterbatch were vacuum-dried at 80 °C for 10 h, then vacuum-dried at 130 °C for 24 h, and finally the PA6 chips and the high-concentration PA6 / micro-nano structured Cu₂O masterbatch were melt-blended and spun to obtain self-assembled micro-nano structured Cu₂O / PA6 antibacterial fibers;

[0135] Among them, the process parameters of the melt-blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3 × 0.75 mm, temperature of the first zone of the screw 258 °C, temperature of the second zone of the screw 272 °C, temperature of the third zone of the screw 266 °C, temperature of the fourth zone of the screw 266 °C, temperature of the GP2 box 266 °C, temperature of the PP2 box 266 °C, temperature of the SP box 266 °C, temperature of the hot roll 67 °C, heat setting temperature 132 °C.

[0136] The finally prepared self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber consists of a PA6 matrix and self-assembled micro-nano structured Cu2O particles with a content of 0.6 wt% dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber immediately after spinning is 66.7, the a value is 0.3, and the b value is 13.5. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 40% for one year, the change rates of the chromaticity L value, a value, and b value are 2.1%, 2.2%, and 3.6% respectively; the antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber against Escherichia coli immediately after spinning is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 56.62%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 40% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 1.2%, 2%, and 0.9% respectively; the single filament fineness of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 6.5 dtex, and the breaking strength is 4.5 cN / dtex.

[0137] Example 6

[0138] A preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber, the specific steps are as follows:

[0139] (1) Preparation of self-assembled micro-nano structured Cu2O particles;

[0140] (1.1) Synthesis of dendritic polymer;

[0141] First, trimellitic acid, 1,2-ethanedithiol, and H2O were mixed in a ratio of 0.16 mol:0.13 mol:100 mL, then heated to 135 °C and held for a period of time until 89% of the H2O was distilled off, then evacuated to 0.098 MPa, and at the same time heated to 155 °C, and held under pressure for 2.2 h to obtain a dendritic polymer;

[0142] The degree of branching DB of the obtained dendritic polymer is 0.55, and the number average molecular weight Mn is 60000 g / mol; the structural formula of the dendritic polymer is: In the formula, the wavy line represents a dendritic polymer that can further react to form more branched units;

[0143] (1.2) Preparation of polyetheramine aqueous solution;

[0144] According to a mass ratio of 1:4, polyetheramine M-600 was added to deionized water, and under the temperature condition of 26 °C, magnetic stirring was carried out at a stirring speed of 360 r / min to fully dissolve and form a polyetheramine aqueous solution;

[0145] (1.3) Keep the stirring speed and temperature constant, and add the dendrimer prepared in step (1.1) into the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system; wherein, the mass ratio of the dendrimer to the polyetheramine is 1:18;

[0146] (1.4) Under the stirring condition with a stirring speed of 360 r / min, add the copper salt solution composed of copper acetate monohydrate and deionized water with a concentration of 0.17 M dropwise into the reaction system through a constant-pressure dropping funnel at a dropping rate of 4 drops per second, and then continue stirring for 1 h; the mass ratio of the copper salt solution to the dendrimer is 1:3;

[0147] (1.5) Under the stirring condition with a stirring speed of 360 r / min, add the aqueous solution of ascorbic acid with a concentration of 0.82 M dropwise into the reaction system through a constant-pressure dropping funnel at a dropping rate of 4 drops per second, and then continue stirring for 3 h; the molar ratio of ascorbic acid to copper ions in the reaction system is 1:2;

[0148] (1.6) Post-treatment;

[0149] Perform suction filtration, washing, and drying to obtain self-assembled micro-nano structured Cu₂O particles;

[0150] The self-assembled micro-nano structured Cu₂O particles are micron-sized spheres assembled from multiple nano-sized Cu₂O particles; wherein, the assembly utilizes the physical and / or chemical forces between dendrimers; the specific surface area of the self-assembled micro-nano structured Cu₂O particles is 50 m 2 ·g -1 ⁻¹; the average particle size of the nano-sized Cu₂O particles is 9.5 nm, and the average particle size of the micron-sized spheres is 1.4 μm;

[0151] (2) Preparation of high-concentration PA6 / micro-nano structured Cu₂O masterbatch;

[0152] First, dry the PA6 powder and the self-assembled micro-nano structured Cu₂O particles at 126 °C for 13 h, then premix the PA6 powder and the self-assembled micro-nano structured Cu₂O particles using a stainless-steel pulverizer for 55 min. The content of the self-assembled micro-nano structured Cu₂O particles in the premixed product is 16 wt%, and finally, perform melt blending and extrusion granulation on the premixed product to obtain the high-concentration PA6 / micro-nano structured Cu₂O masterbatch; wherein, the melt blending is carried out using a twin-screw extruder, and the temperatures of the first to fifth zones of the twin-screw extruder are 235 °C, 253 °C, 253 °C, 253 °C, 253 °C respectively, the head temperature is 262 °C, and the screw speed is 173 rpm;

[0153] (3) Preparation of self-assembled micro-nano structured Cu₂O / PA6 antibacterial fibers;

[0154] First, slice the PA6 and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are vacuum dried at 80 °C for 10 h, and then vacuum dried at 130 °C for 24 h. Finally, the PA6 slices and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are melt-blended and spun to obtain self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0155] Among them, the process parameters of the melt-blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 260 °C, temperature of the second zone of the screw 273 °C, temperature of the third zone of the screw 267 °C, temperature of the fourth zone of the screw 267 °C, temperature of the GP2 box 267 °C, temperature of the PP2 box 267 °C, temperature of the SP box 267 °C, temperature of the hot roller 67 °C, heat setting temperature 133 °C.

[0156] The finally obtained self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers are composed of a PA6 matrix and self-assembled micro-nano structured Cu2O particles with a content of 0.7 wt% dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers at the end of spinning is 66.72, the a value is 0.31, and the b value is 13.7. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 50% for one year, the change rates of the chromaticity L value, a value, and b value are 2.9%, 3.6%, and 3.2% respectively; the antibacterial rates of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers against Escherichia coli, Staphylococcus aureus, and Candida albicans at the end of spinning are 99.999%, 99.999%, and 59.28% respectively. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 50% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 1.5%, 1.3%, and 1.6% respectively; the single filament fineness of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers is 7.5 dtex, and the breaking strength is 4.8 cN / dtex.

[0157] Example 7

[0158] A preparation method of self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers, the specific steps are as follows:

[0159] (1) Preparation of self-assembled micro-nano structured Cu2O particles;

[0160] (1.1) Synthesis of dendritic polymers;

[0161] First, benzene-1,3,5-tricarboxylic acid, 1,2-ethanedithiol and H2O were mixed in a ratio of 0.18 mol: 0.14 mol: 100 mL, and then the temperature was raised to 140 °C and held for a period of time until 93% of the H2O was distilled off. Then, the vacuum was pumped to 0.098 MPa while the temperature was raised to 158 °C, and the reaction was carried out under constant temperature and pressure for 2.1 h to obtain a dendritic polymer.

[0162] The degree of branching DB of the obtained dendritic polymer was 0.49, and the number-average molecular weight Mn was 57000 g / mol; the structural formula of the dendritic polymer was: In the formula, the wavy line represents a dendritic polymer that can further react to form more branched units;

[0163] (1.2) Prepare an aqueous solution of polyetheramine;

[0164] According to a mass ratio of 1:5, polyetheramine M-600 was added to deionized water, and under the temperature condition of 28 °C, magnetic stirring was carried out at a stirring speed of 330 r / min to fully dissolve and form an aqueous solution of polyetheramine.

[0165] (1.3) Keeping the stirring speed and temperature unchanged, the dendritic polymer prepared in step (1.1) was added to the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system; among them, the mass ratio of the dendritic polymer to polyetheramine was 1:19.

[0166] (1.4) Under the stirring condition of a stirring speed of 330 r / min, a copper salt solution composed of copper acetate monohydrate and deionized water with a concentration of 0.172 M was added dropwise to the reaction system through a constant-pressure dropping funnel at a dropping rate of 4 drops / second, and then stirring was continued for 1 h; the mass ratio of the copper salt solution to the dendritic polymer was 1:3.

[0167] (1.5) Under the stirring condition of a stirring speed of 380 r / min, an aqueous solution of ascorbic acid with a concentration of 0.84 M was added dropwise to the reaction system through a constant-pressure dropping funnel at a dropping rate of 4 drops / second, and then stirring was continued for 3 h; the molar ratio of ascorbic acid to copper ions in the reaction system was 1:2.

[0168] (1.6) Post-treatment;

[0169] Suction filtration, washing and drying were carried out to obtain self-assembled micro-nano structured Cu2O particles;

[0170] The self-assembled micro-nano structured Cu2O particles were micron-sized spheres assembled from multiple nano-sized Cu2O particles; among them, the assembly utilized the physical and / or chemical forces between dendritic polymers; the specific surface area of the self-assembled micro-nano structured Cu2O particles was 55 m 2 ·g -1; The average particle size of the nanoscale Cu2O particles is 9.8 nm, and the average particle size of the micron-scale spheres is 1.5 μm;

[0171] (2) Preparation of high-concentration PA6 / micro-nano structured Cu2O masterbatch;

[0172] First, the PA6 chips and the self-assembled micro-nano structured Cu2O particles are dried at 128 °C for 12 h, then premixed using a stainless steel crusher for 57 min. The content of the self-assembled micro-nano structured Cu2O particles in the premixed product is 18 wt%. Finally, the premixed product is melt-blended and pelletized to obtain the high-concentration PA6 / micro-nano structured Cu2O masterbatch. Among them, the melt-blending is carried out using a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder are 235 °C, 253 °C, 253 °C, 253 °C, 253 °C respectively, the head temperature is 264 °C, and the screw speed is 178 rpm;

[0173] (3) Preparation of self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0174] First, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are vacuum-dried at 80 °C for 10 h, then vacuum-dried at 130 °C for 24 h. Finally, the PA6 chips and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are melt-blended and spun to obtain the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0175] Among them, the process parameters of the melt-blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 263 °C, temperature of the second zone of the screw 274 °C, temperature of the third zone of the screw 267 °C, temperature of the fourth zone of the screw 267 °C, temperature of the GP2 box 267 °C, temperature of the PP2 box 267 °C, temperature of the SP box 267 °C, temperature of the hot roller 68 °C, heat setting temperature 134 °C.

[0176] The finally prepared self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is composed of a PA6 matrix and self-assembled micro-nano structured Cu2O particles with a content of 0.9 wt% dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber at the end of spinning is 66.77, the a value is 0.31, and the b value is 13.9. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 65% for one year, the change rates of the chromaticity L value, a value, and b value are 2.3%, 3.5%, and 2.2% respectively; the antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber against Escherichia coli at the end of spinning is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 65.37%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 65% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 2%, 0.9%, and 1.3% respectively; the denier of the single filament of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 7.8 dtex, and the breaking strength is 5.3 cN / dtex.

[0177] Example 8

[0178] A preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is as follows:

[0179] (1) Preparation of self-assembled micro-nano structured Cu2O particles;

[0180] (1.1) Synthesis of dendritic polymer;

[0181] First, trimellitic acid, 1,2-ethanedithiol, and H2O were mixed in a ratio of 0.2 mol:0.15 mol:100 mL, then heated to 150 °C and kept warm for a period of time until 95% of the H2O was distilled off. Then, the vacuum was pumped to 0.098 MPa, and at the same time, the temperature was raised to 165 °C, and the reaction was carried out under constant temperature and pressure for 2 h to obtain a dendritic polymer;

[0182] The degree of branching DB of the obtained dendritic polymer is 0.5, and the number-average molecular weight Mn is 58950 g / mol; the structural formula of the dendritic polymer is: In the formula, the wavy line represents a dendritic polymer that can further react to form more branched units;

[0183] (1.2) Preparation of polyetheramine aqueous solution;

[0184] According to a mass ratio of 1:6, polyetheramine M-600 was added to deionized water, and under the temperature condition of 30 °C, magnetic stirring was carried out at a stirring speed of 300 r / min to fully dissolve and form a polyetheramine aqueous solution;

[0185] (1.3) Keep the stirring speed and temperature constant, and add the dendrimer polymer prepared in step (1.1) to the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system; wherein, the mass ratio of the dendrimer polymer to polyetheramine is 1:20;

[0186] (1.4) Under the stirring condition with a stirring speed of 300 r / min, add the copper salt solution composed of copper acetate monohydrate and deionized water with a concentration of 0.175 M to the reaction system dropwise through a constant pressure dropping funnel at a dropping rate of 4 drops per second, and then continue stirring for 1 h; the mass ratio of the copper salt solution to the dendrimer polymer is 1:3;

[0187] (1.5) Under the stirring condition with a stirring speed of 400 r / min, add the aqueous solution of ascorbic acid with a concentration of 0.875 M to the reaction system dropwise through a constant pressure dropping funnel at a dropping rate of 4 drops per second, and then continue stirring for 3 h; the molar ratio of ascorbic acid to copper ions in the reaction system is 1:2;

[0188] (1.6) Post-treatment;

[0189] Perform suction filtration, washing and drying to obtain self-assembled micro-nano structured Cu₂O particles;

[0190] The self-assembled micro-nano structured Cu₂O particles are micron-sized spheres formed by assembling multiple nano-sized Cu₂O particles; wherein, the assembly utilizes the physical and / or chemical forces between dendrimer polymers; the specific surface area of the self-assembled micro-nano structured Cu₂O particles is 60 m 2 ·g -1 ⁻¹; the average particle size of the nano-sized Cu₂O particles is 10 nm, and the average particle size of the micron-sized spheres is 1.6 μm;

[0191] (2) Preparation of high-concentration PA6 / micro-nano structured Cu₂O masterbatch;

[0192] First, dry the PA6 chips and the self-assembled micro-nano structured Cu₂O particles at 130 °C for 12 h, then premix the PA6 chips and the self-assembled micro-nano structured Cu₂O particles using a stainless steel pulverizer for 60 min. The content of the self-assembled micro-nano structured Cu₂O particles in the premixed product is 20 wt%. Finally, perform melt blending and extrusion granulation on the premixed product to obtain the high-concentration PA6 / micro-nano structured Cu₂O masterbatch; wherein, the melt blending is carried out using a twin-screw extruder. The temperatures of the first to fifth zones of the twin-screw extruder are 235 °C, 253 °C, 253 °C, 253 °C, 253 °C respectively, the head temperature is 265 °C, and the screw speed is 180 rpm;

[0193] (3) Preparation of self-assembled micro-nano structured Cu₂O / PA6 antibacterial fibers;

[0194] First, slice the PA6 and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are vacuum dried at 80 °C for 10 h, then vacuum dried at 130 °C for 24 h. Finally, the PA6 slices and the high-concentration PA6 / micro-nano structured Cu2O masterbatch are melt-blended and spun to obtain self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers;

[0195] Among them, the process parameters of melt-blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 265 °C, temperature of the second zone of the screw 275 °C, temperature of the third zone of the screw 268 °C, temperature of the fourth zone of the screw 268 °C, temperature of the GP2 box 268 °C, temperature of the PP2 box 268 °C, temperature of the SP box 268 °C, temperature of the hot roller 68 °C, heat setting temperature 135 °C.

[0196] The finally obtained self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers are composed of a PA6 matrix and self-assembled micro-nano structured Cu2O particles with a content of 1 wt% dispersed therein; the chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers at the end of spinning is 66.8, the a value is 0.32, and the b value is 14.3. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 80% for one year, the change rates of the chromaticity L value, a value, and b value are 3.7%, 3.2%, and 2.9% respectively; the antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers against Escherichia coli at the end of spinning is 99.999%, the antibacterial rate against Staphylococcus aureus is 99.999%, and the antibacterial rate against Candida albicans is 74.45%. After being placed in an indoor environment at a temperature of 25 °C and a relative humidity of 80% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are 1.6%, 1.5%, and 2% respectively; the single filament fineness of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers is 8 dtex, and the breaking strength is 5.5 cN / dtex.

Claims

1. A self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber, characterized in that, It mainly consists of a PA6 matrix and self-assembled micro-nano structured Cu2O particles dispersed therein; The self-assembled micro-nano structured Cu2O particles are micron-scale spheres formed by assembling multiple nano-scale Cu2O particles, wherein the assembly utilizes the physical and / or chemical forces between dendritic polymers; The structural formula of the dendritic polymer is as follows: In the formula, the wavy line represents a dendritic polymer that can further react to form more branched units; The chromaticity L value of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber immediately after spinning is 66.62 - 66.80, the a value is 0.29 - 0.32, and the b value is 13.3 - 14.

3. After being placed in an indoor environment at 25°C and a relative humidity of 40% - 80% for one year, the change rates of the chromaticity L value, a value, and b value are all less than 4%; The antibacterial rate of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber against Escherichia coli is >99.99% immediately after spinning, the antibacterial rate against Staphylococcus aureus is >99.99%, and the antibacterial rate against Candida albicans is ≥50%. After being placed in an indoor environment at 25°C and a relative humidity of 40% - 80% for one year, the change rates of the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are all less than 2%.

2. The self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 1, wherein The content of the self-assembled micro-nano structured Cu2O particles in the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 0.4 - 1.2 wt%; the single filament fineness of the self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is 5.6 - 8.0 dtex, and the breaking strength is 4.0 - 5.5 cN / dtex; the antibacterial rate of the self-assembled micro-nano structured Cu2O particles against Escherichia coli is above 99.999%, the antibacterial rate against Staphylococcus aureus is above 99.999%, the antibacterial rate against Candida albicans is above 97.29%, the antibacterial rate against methicillin-resistant Staphylococcus aureus is above 99.999%, and the antibacterial rate against vancomycin-resistant Enterococcus is above 99.999%.

3. The self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 1, characterized in that, The average particle size of the nano-scale Cu2O particles is 8 - 10 nm, and the average particle size of the micron-scale spheres is 1.0 - 1.6 μm.

4. The self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 1, wherein, The degree of branching DB of the dendritic polymer is 0.45 - 0.55, and the number average molecular weight Mn is 45000 - 60000 g / mol.

5. The self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 1, characterized in that, The specific surface area of the self-assembled micro-nano structured Cu2O particles is 30 - 60 m 2 ·g -1 , and the content of the dendritic polymer in the self-assembled micro-nano structured Cu2O particles is 23.2 - 24.2 wt%.

6. A preparation method of self-assembled micro-nano structured Cu2O / PA6 antibacterial fibers, characterized in that, The self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber is prepared by melt-blending and spinning PA6 chips with a high-concentration PA6 / micro-nano structured Cu2O masterbatch; The content of the self-assembled micro-nano structured Cu2O particles in the high-concentration PA6 / micro-nano structured Cu2O masterbatch is 10 - 20 wt%; The preparation process of the self-assembled micro-nano structured Cu2O particles is as follows: First, a dendritic polymer is synthesized by the A2 + B3 method using benzene-1,2,3-tricarboxylic acid and 1,2-ethanedithiol as raw materials. Then, the dendritic polymer is added to an aqueous solution of polyetheramine to form a homogeneous and transparent reaction system. Next, a copper salt solution is dropped into the reaction system under stirring conditions and then stirred for a period of time. Finally, an aqueous solution of ascorbic acid is dropped into the reaction system under stirring conditions and then stirred for a period of time to obtain the self-assembled micro-nano structured Cu2O particles.

7. The preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 6, characterized in that, The mass ratio of PA6 chips to high-concentration PA6 / micro-nano structured Cu2O masterbatch is 5-10:1; before melt blending and spinning, the PA6 chips and high-concentration PA6 / micro-nano structured Cu2O masterbatch are dried. The drying process is as follows: first, vacuum dry at 80 °C for 10 h, and then vacuum dry at 130 °C for 24 h; the process parameters of melt blending and spinning include: winding speed 800 m / min, number of spinneret holes 36, hole size 0.3×0.75 mm, temperature of the first zone of the screw 255-265 °C, temperature of the second zone of the screw 270-275 °C, temperature of the third zone of the screw 265-268 °C, temperature of the fourth zone of the screw 265-268 °C, temperature of the GP2 box 265-268 °C, temperature of the PP2 box 265-268 °C, temperature of the SP box 264-268 °C, temperature of the hot roller 65-68 °C, heat setting temperature 130-135 °C.

8. The preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 6, characterized in that, The preparation process of the high-concentration PA6 / micro-nano structured Cu2O masterbatch is as follows: first, premix the PA6 powder or chips and the self-assembled micro-nano structured Cu2O particles. The content of the self-assembled micro-nano structured Cu2O particles in the premixed product is 10-20 wt%, and then melt blend and extrude granulate the premixed product to obtain the high-concentration PA6 / micro-nano structured Cu2O masterbatch.

9. The preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 6, characterized in that, The preparation steps of the self-assembled micro-nano structured Cu2O particles are as follows: (1) Synthesize dendritic polymers; First, mix the benzene-1,2,3-tricarboxylic acid, the 1,2-ethanedithiol and H2O in a ratio of 0.1-0.2 mol:0.1-0.15 mol:100 mL, then heat up to 120-150 °C and keep warm for a period of time until more than 80% of the H2O is distilled out, then evacuate to 0.098 MPa, and at the same time heat up to 145-165 °C, keep warm and under pressure for reaction for 2-2.5 h to obtain dendritic polymers; (2) Prepare an aqueous solution of polyetheramine; Add polyetheramine to deionized water, and magnetically stir under the temperature condition of 20-30 °C to fully dissolve to form an aqueous solution of polyetheramine; (3) Keep the stirring speed and temperature unchanged, and add the dendritic polymers to the aqueous solution of polyetheramine to form a homogeneous and transparent reaction system; (4) Under stirring conditions, add the copper salt solution dropwise to the reaction system through a constant pressure dropping funnel, and then continue stirring for 1 h; (5) Under stirring conditions, add the aqueous solution of ascorbic acid dropwise to the reaction system through a constant pressure dropping funnel, and then continue stirring for 2-3 h; (6) Post-treatment; Filter by suction, wash and dry to obtain the self-assembled micro-nano structured Cu2O particles.

10. The preparation method of a self-assembled micro-nano structured Cu2O / PA6 antibacterial fiber according to claim 9, characterized in that, In step (2), the polyetheramine is polyetheramine M-600; the mass ratio of polyetheramine to deionized water is 1:4-6; the stirring speed is 300-400 r / min; In step (3), the mass ratio of dendritic polymers to polyetheramine is 1:15-20; In step (4), the stirring speed is 300-400 r / min; the concentration of the copper salt solution is 0.15-0.175 M and is composed of copper acetate monohydrate and deionized water; the dropping rate is 3-4 seconds / drop; the mass ratio of the copper salt solution to the dendritic polymers is 1:2-3; In step (5), the stirring speed is 300 - 400 r / min; the concentration of the ascorbic acid aqueous solution is 0.7 - 0.875 M; the molar ratio of ascorbic acid to copper ions in the reaction system is 1:2; the dropping rate is 3 - 4 seconds per drop.

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