Highly moisture-absorbing and antibacterial composite nanofiber membrane, and preparation method and application thereof

Abstract

The application discloses a kind of high moisture-absorbing antibacterial composite nanofiber membrane and its preparation method and application, including silver nitrate solution is added to amination cyclodextrin solution, the pH of reaction solution is adjusted, after reaction is finished, multiple washing and centrifugation, obtain amination cyclodextrin nanometer silver supramolecular assembly structure, which is together with polyacrylonitrile, polyvinyl alcohol is prepared composite spinning solution and carries out electrostatic spinning, obtains composite nanofiber membrane;With binary aldehyde, composite nanofiber membrane is grafted and crosslinked, after ending, vacuum drying is obtained, and the high moisture-absorbing antibacterial composite nanofiber membrane with crosslinked structure is obtained.The application is wrapped by amination cyclodextrin silver nanoparticles, and the composite nanofiber membrane with crosslinked structure is prepared by binary aldehyde, not only solves the problem that free nanometer silver particles are easy to lose, but also improves the moisture-absorbing property, antibacterial property, coloring property and mechanical property of fiber, meets the demand of high moisture-absorbing antibacterial functional fiber in market, especially in the field of functional textiles.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanofiber membranes, in particular to a high-hygroscopic antibacterial composite nanofiber membrane and a preparation method and application thereof. BACKGROUND

[0002] With the development of social technology and the continuous improvement of living standards, people's pursuit of textile consumption is no longer only practicality and durability, but more concerned about comfort and environmental protection. Polyacrylonitrile is a high molecular polymer copolymerized by more than 85% of acrylonitrile and other second and third monomers, and polyacrylonitrile fiber is also known as acrylic fiber, which is known as artificial wool. Its textiles are widely used in clothing, decoration, industry and other fields, but polyacrylonitrile has a large number of strong polar nitrile groups, which leads to strong interaction between molecular chains, poor water absorption and moisture absorption performance, and strong static effect, which seriously limits its wide application.

[0003] It is of great significance to modify polyacrylonitrile with polyhydroxy compounds for the functionalization of polyacrylonitrile fibers. Polyvinyl alcohol (PVA) is a water-soluble polymer. Due to the presence of abundant hydroxyl groups, PVA composite fibers are expected to have good hydrophilicity, spinnability and mechanical properties. In the prior art, polyvinyl alcohol is easily expanded in water and has insufficient stability, so it is often modified by crosslinking and other methods to have good mechanical properties.

[0004] Nanoscale silver particles have extremely high surface energy and great chemical activity, and their ability to adsorb bacteria and viruses is greatly improved, and their antibacterial activity is also greatly enhanced. As a broad-spectrum antibacterial agent, it has always attracted widespread attention. The outer edge of the molecular structure of cyclodextrin contains a large number of hydroxyl groups, which can be adsorbed on the surface of metal during the synthesis of metal nanoparticles, thereby effectively stabilizing the metal nanoparticles and improving the biocompatibility of the metal nanoparticles. Natural cyclodextrin has problems of insufficient water solubility and reactivity, which limits its practical application. Under the condition that the basic skeleton of cyclodextrin ring is kept unchanged, the aminated cyclodextrin obtained by introducing amino groups into the cyclodextrin molecule by chemical method has better application prospect. At the same time, cyclodextrin has a hydrophobic cavity, which can adsorb dyes by host-guest inclusion to improve the coloring property of the fiber.

[0005] Electrospinning technology is a simple and low-cost preparation technology of polymer nanofiber. Its basic principle is that under the action of tens of kilovolts electric field, the droplet at the needle tip will change from spherical to conical shape by overcoming surface tension, and the fiber filament will be obtained by extending from the conical tip, and the nanofiber material will be formed on the receiver. Compared with the fibers prepared by traditional methods, the nanofiber membrane prepared by electrospinning technology has larger porosity and specific surface area, and can be more widely applied in various fields, and has good development prospect. SUMMARY

[0006] The main object of the present application is to provide a preparation method of high moisture absorption and antibacterial composite nanofiber membrane, by introducing amine cyclodextrin wrapped nano silver particles, and preparing a composite nanofiber membrane with cross-linked structure from a binary aldehyde, the obtained fiber membrane has the functions of strong water absorption, good dye adsorption and coloring, excellent mechanical properties and excellent antibacterial performance, solves the problems of poor water absorption and single function of traditional polyacrylonitrile fiber, meets the requirements of people on antibacterial aspect, and the raw material source is rich, the process is simple and controllable, and it is green and environmental protection.

[0007] The second object of the present application is to provide a high moisture absorption and antibacterial composite nanofiber membrane obtained by the above preparation method, which has the functions of strong water absorption, good dye adsorption and coloring, excellent mechanical properties and excellent antibacterial performance.

[0008] The third object of the present application is to provide the application of the above high moisture absorption and antibacterial composite nanofiber membrane in functional textiles.

[0009] In order to achieve the above-mentioned objects, the following technical scheme is adopted:

[0010] The present application provides a preparation method of high moisture absorption and antibacterial composite nanofiber membrane, comprising the following steps:

[0011] (1) silver nitrate solution is added to amine cyclodextrin solution, sodium hydroxide solution is used to adjust the pH of the reaction solution, the reaction temperature, pH and stirring time are controlled, and after the reaction is completed, multiple washing and centrifugation are carried out to obtain amine cyclodextrin nanosilver super molecular assembly structure;

[0012] (2) using aprotic polar solvent, the amine cyclodextrin nanosilver super molecular assembly structure obtained in step (1) is prepared together with polyacrylonitrile and polyvinyl alcohol to prepare a composite spinning solution, and an electrospinning process is used to prepare a composite nanofiber membrane;

[0013] (3) in an acidic solution, the composite nanofiber membrane obtained in step (2) is grafted and cross-linked by using a binary aldehyde, and after the reaction is completed, vacuum drying is carried out to obtain a high moisture absorption and antibacterial composite nanofiber membrane with cross-linked structure.

[0014] Preferably, in step (1), the amine cyclodextrin is obtained by first sulfonating cyclodextrin with 4-methylbenzenesulfonyl chloride reagent, and then treating with an amine reagent, wherein the amine reagent is selected from one of ethylenediamine, diethylenetriamine and triethylenetetramine; the cyclodextrin is selected from one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.

[0015] Preferably, in step (1), the concentration of the silver nitrate solution is 0.05-5 mmol / L, more preferably one of 0.1 mmol / L, 0.2 mmol / L, 0.3 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.6 mmol / L, 0.7 mmol / L, 0.8 mmol / L, 0.9 mmol / L, 1 mmol / L; the concentration of the aminated cyclodextrin solution is 0.5-10 mmol / L, more preferably one of 1 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L.

[0016] Preferably, in step (1), the reaction temperature is 20-100℃, selected from one of 50℃, 55℃, 60℃, 65℃, 70℃.

[0017] Preferably, in step (1), the reaction time is 0.5h-10h, selected from one of 2h, 3h, 4h, 5h, 6h.

[0018] Preferably, in step (1), the pH of the reaction solution is 3-14, selected from one of 5, 6, 7, 8, 9, 10, 11, 12.

[0019] Preferably, in step (1), the stirring speed is 30-300r / min, selected from one of 80r / min, 100r / min, 120r / min, 140r / min, 160r / min.

[0020] Preferably, in step (1), the centrifugal rate is 3000-15000rpm, selected from one of 5000rpm, 6000rpm, 7000rpm, 8000rpm, 9000rpm, 10000rpm.

[0021] Preferably, in step (1), the centrifugal time is 10-60min, selected from one of 15min, 20min, 25min, 30min, 35min, 40min.

[0022] Preferably, in step (2), the aprotic polar solvent is selected from one of N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide.

[0023] Preferably, in step (2), the weight average molecular weight of the polyacrylonitrile is 5-20w; more preferably one of 8w, 9w, 10w, 11w, 12w, 13w, 14w, 15w.

[0024] Preferably, in step (2), the weight average molecular weight of the polyvinyl alcohol is 3-15w; more preferably one of 5w, 6w, 7w, 8w, 9w, 10w, 11w, 12w.

[0025] Preferably, in step (2), the concentration of polyacrylonitrile in the composite spinning solution is 5%-40% by mass.

[0026] Preferably, in step (2), the mass ratio of polyvinyl alcohol to polyacrylonitrile is 1:10-1:1 by mass; more preferably one of 3:10, 4:10, 5:10, 6:10, 7:10, 8:10.

[0027] Preferably, in step (2), the mass ratio of aminated cyclodextrin nanosilver to polyacrylonitrile is 1:50-1:10 by mass; more preferably one of 1:25, 1:24, 1:23:1:22, 1:21, 1:20.

[0028] Preferably, in step (2), the stirring temperature of the spinning solution is 20-60°C; the stirring time is 6-24h; and the stirring speed is 200-800r / min.

[0029] Preferably, in step (2), the voltage of the electrospinning process is 10-50kV, the fiber receiving distance is 10-35cm, the outflow speed of the spinning solution is 0.1-3mL / h, the inner diameter of the spinning needle is 0.2-2mm, the spinning temperature is 20-70°C, and the relative humidity is 10%-25%.

[0030] Preferably, in step (2), the composite nanofiber membrane further comprises a vacuum drying step, and the drying temperature is 40-100°C and the drying time is 0.5-12h.

[0031] Preferably, in step (3), the concentration of the sulfuric acid solution is 0.01-0.1M; more preferably one of 0.01M, 0.02M, 0.03M, 0.04M, 0.05M.

[0032] Preferably, in step (3), the dialdehyde is selected from one of malondialdehyde, glutaraldehyde, and adipaldehyde.

[0033] Preferably, in step (3), the amount of dialdehyde added is 0.01%-10% of the composite fiber membrane by mass; more preferably one of 1%, 2%, 3%, 4%, 5%.

[0034] Preferably, in step (3), the crosslinking time of the fiber membrane is 0.5-12h.

[0035] Preferably, in step (3), the cross-linking temperature of the fiber membrane is 30-90℃; more preferably one of 50℃, 55℃, 60℃, 65℃, 70℃, 75℃.

[0036] Preferably, in step (3), the drying temperature of the composite nanofiber membrane with cross-linking structure is 40-100℃, and the drying time is 0.5-12h.

[0037] The application also provides a high-hygroscopic antibacterial composite nanofiber membrane with a cross-linking structure of cyclodextrin nanosilver supermolecular assembly, which is obtained by the preparation method of the aforementioned high-hygroscopic antibacterial composite nanofiber membrane.

[0038] The application also provides an application of the aforementioned high-hygroscopic antibacterial composite nanofiber membrane in functional textiles, such as medical protective textile products.

[0039] Compared with the prior art, the application has the following beneficial effects:

[0040] 1. The application uses aminated cyclodextrin as a stabilizer and reducing agent to prepare silver nanoparticles with uniform particle size by an in-situ reduction method, and the synthesis method is simple in process and friendly to the environment, which provides a new idea for green synthesis of metal nanoparticles. The aminated cyclodextrin gives the cyclodextrin stronger reducibility, so that the aminated cyclodextrin is more easily protonated and has good complexing ability with negatively charged guest molecules, and is an excellent intermediate for building supermolecular structures. The introduction of aminated cyclodextrin silver nanoparticles into the nanofiber membrane solves the problem of easy loss of free aminated cyclodextrin silver nanoparticles through cross-linking, so that the fiber has excellent water absorption, good mechanical properties and coloring ability, and excellent antibacterial performance, meeting the demand of people for antibacterial functional fibers.

[0041] 2. The application prepares a high-hygroscopic antibacterial composite nanofiber membrane with large specific surface area, strong water absorption, good air permeability, good dye adsorption (coloring) and excellent antibacterial performance by an electrospinning technology, and the synthesis process is simple, the raw materials are abundant, and the application prospect is good. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 It is a schematic diagram of the principle of preparing the high-hygroscopic antibacterial composite nanofiber membrane in Example 1.

[0043] Figure 2 It is a SEM image of the high-hygroscopic antibacterial composite nanofiber membrane in Example 1.

[0044] Figure 3 It is a schematic diagram of the antibacterial ability comparison of the composite nanofiber membranes in Examples 1-4 and the comparative example.

[0045] Figure 4A schematic diagram for comparing the moisture absorption capacity of the composite nanofiber membrane in Examples 1-4 and Comparative Example. DETAILED DESCRIPTION

[0046] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be described clearly and completely below with reference to the drawings of the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the described embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without any inventive effort fall within the protection scope of the present application.

[0047] Example 1

[0048] As shown in the following table, the present embodiment provides a preparation method of a high-moisture-absorption antibacterial composite nanofiber membrane, and the specific steps are as follows: Figure 1

[0049] Step 1: Prepare a 1 mmol / L silver nitrate solution, and add ethylenediamine aminated cyclodextrin α-CD-6-EN to the silver nitrate solution to make the concentration of α-CD-6-EN reach 5 mmol / L. Adjust the pH of the reaction solution to 8 with sodium hydroxide solution, control the reaction temperature to be 60°C, the stirring rate to be 100 r / min, and the reaction time to be 2 h. After the reaction is completed, ethylenediamine aminated cyclodextrin wrapped nanosilver particles are obtained by centrifugation at a speed of 8000 rpm for 30 min.

[0050] Step 2: Weigh 5 g of polyacrylonitrile with a weight average molecular weight of 10 w and 1.5 g of polyvinyl alcohol with a weight average molecular weight of 6 w, and add them to 50 g of N,N-dimethylformamide. Further, 0.2 g of ethylenediamine aminated cyclodextrin nanosilver particles are added to the solution. Stir at 25°C at a speed of 200 r / min for 8 h to obtain a uniform composite spinning solution.

[0051] Step 3: The above composite spinning solution is loaded into a push pump matched with the electrospinning equipment, a needle with an inner diameter of 1.2 mm is selected, the electrospinning voltage is set to 10 kV, the receiving distance is set to 10 cm, the spinning speed is set to 0.5 mL / h, the spinning temperature is set to 20°C, the relative humidity is set to 10%, and the spinning time is set to 3.5 h. A composite nanofiber membrane is obtained on a metal receiving plate with tin foil paper, and the fiber membrane is dried in a vacuum oven at 60°C for 8 h.

[0052] ​Step 4: Prepare a cross-linking solution, take 50 mL of 0.01 M sulfuric acid solution, take 2 g of the above obtained composite fiber membrane and immerse it in the sulfuric acid solution, and further add 0.02 g of glutaraldehyde to it. After constant temperature immersion and cross-linking at 50°C for 6 h, the fiber membrane is dried in a vacuum oven at 60°C for 8 h to obtain a cyclodextrin nano-silver supramolecular assembly structure composite nanofiber membrane with a cross-linked structure, and the SEM image thereof is shown in Figure 2

[0053] Example 2

[0054] The present embodiment provides a preparation method of a high-hygroscopic antibacterial composite nanofiber membrane, and the specific steps are as follows:

[0055] Step 1: Prepare a 0.9 mmol / L silver nitrate solution, add diethylenetriamine aminated cyclodextrin β-CD-6-DIEN to the silver nitrate solution to make the concentration of β-CD-6-DIEN reach 4 mmol / L. Adjust the pH of the reaction solution to 10 with sodium hydroxide solution, control the reaction temperature to be 70°C, the stirring rate to be 120 r / min, and the reaction time to be 4 h. After the reaction is completed, centrifuge at a speed of 10000 rpm for 20 min to obtain diethylenetriamine aminated cyclodextrin wrapped nano-silver particles.

[0056] Step 2: Take 6 g of polyacrylonitrile with a weight average molecular weight of 12w and 2 g of polyvinyl alcohol with a weight average molecular weight of 8w, and add them to 50 g of N,N-dimethylformamide. Further add 0.3 g of diethylenetriamine aminated cyclodextrin nano-silver particles to the solution. Stir at a constant temperature of 40°C and a speed of 400 r / min for 12 h to obtain a uniform composite spinning solution.

[0057] Step 3: Load the above-mentioned composite spinning solution into a push pump matched with the electrospinning equipment, select a needle with an inner diameter of 0.84 mm, set the electrospinning voltage to be 14 kV, the receiving distance to be 15 cm, the spinning speed to be 1.2 mL / h, the spinning temperature to be 30°C, the relative humidity to be 20%, and the spinning time to be 4.5 h. Obtain a composite nanofiber membrane on a metal receiving plate with tin foil paper, and dry the fiber membrane in a vacuum oven at 70°C for 10 h.

[0058] Step 4: Prepare a cross-linking solution, take 65 mL of 0.03 M sulfuric acid solution, take 2 g of the above obtained composite fiber membrane and immerse it in the sulfuric acid solution, and further add 0.04 g of glutaraldehyde to it. After constant temperature immersion and cross-linking at 60°C for 8 h, the fiber membrane is dried in a vacuum oven at 70°C for 10 h to obtain a cyclodextrin nano-silver supramolecular assembly structure composite nanofiber membrane with a cross-linked structure.

[0059] Example 3

[0060] ​The embodiment provides a preparation method of a high-hygroscopic antibacterial composite nanofiber membrane, and the specific steps are as follows.

[0061] Step 1: prepare a 0.8 mmol / L silver nitrate solution, add triethylenetetramine aminated cyclodextrin γ-CD-6-TRIEN to the silver nitrate solution, so that the concentration of γ-CD-6-TRIEN reaches 3 mmol / L, adjust the pH of the reaction solution to 12 by using a sodium hydroxide solution, control the reaction temperature to be 65 DEG C, the stirring speed is 110 r / min, and the reaction time is 3 h. After the reaction is completed, triethylenetetramine aminated cyclodextrin wrapped silver nanoparticles are obtained by centrifugation at a speed of 12000 rpm for 40 min.

[0062] Step 2: weigh 7g of polyacrylonitrile with a weight average molecular weight of 13w and 3g of polyvinyl alcohol with a weight average molecular weight of 10w, and add them to 50g of N,N-dimethylformamide, and further add 0.25g of aminated cyclodextrin silver nanoparticles to the solution. Stir at 300 r / min for 10h at 30 DEG C to obtain a uniform composite spinning solution.

[0063] Step 3: the above-mentioned composite spinning solution is loaded into a push pump matched with an electrospinning device, a needle with an inner diameter of 1.12mm is selected, the electrospinning voltage is set to 12kV, the receiving distance is set to 12cm, the spinning speed is set to 1mL / h, the spinning temperature is set to 25 DEG C, the relative humidity is set to 15%, and the spinning time is set to 4h, and a composite nanofiber membrane is obtained on a metal receiving plate with tin foil paper, and the fiber membrane is dried in a vacuum oven at 65 DEG C for 9h.

[0064] Step 4: prepare a crosslinking solution, take 60mL of 0.02M sulfuric acid solution, take 2g of the above-mentioned composite fiber membrane, immerse the fiber membrane in the sulfuric acid solution, and further add 0.03g of glutaraldehyde. After constant-temperature immersion crosslinking at 55 DEG C for 7h, the fiber membrane is vacuum dried at 65 DEG C for 9h, and a cyclodextrin silver supramolecular assembly structure composite nanofiber membrane with a crosslinked structure is obtained.

[0065] Example 4

[0066] The embodiment provides a preparation method of a high-hygroscopic antibacterial composite nanofiber membrane, and the specific steps are as follows:

[0067] Step 1: A 0.7 mmol / L silver nitrate solution was prepared, and diethylenetriamine-aminated cyclodextrin β-CD-6-EN was added to the silver nitrate solution to make the concentration of β-CD-6-EN reach 2 mmol / L. The pH of the reaction solution was adjusted to 9 with a sodium hydroxide solution, the reaction temperature was controlled at 60°C, the stirring rate was 120 r / min, and the reaction time was 4 h. After the reaction was completed, the ethylenediamine-aminated cyclodextrin wrapped silver nanoparticle was obtained by centrifugation at a speed of 12000 rpm for 30 min.

[0068] Step 2: 6.5 g of polyacrylonitrile with a weight average molecular weight of 15 w and 2.5 g of polyvinyl alcohol with a weight average molecular weight of 10 w were weighed and added to 50 g of N,N-dimethylformamide. Then, 0.3 g of aminated cyclodextrin silver nanoparticles were added to the solution. The solution was stirred at 50°C at a constant temperature for 15 h at a speed of 450 r / min to obtain a uniform composite spinning solution.

[0069] Step 3: The above composite spinning solution was loaded into a push pump matched with the electrospinning equipment. A needle with an inner diameter of 0.75 mm was selected, and the electrospinning voltage was set to 15 kV, the receiving distance was 18 cm, the spinning speed was 1.5 mL / h, the spinning temperature was 35°C, the relative humidity was 25%, and the spinning time was 5 h. A composite nanofiber membrane was obtained on a metal receiving plate with tin foil paper. The fiber membrane was dried in a vacuum oven at 80°C for 12 h.

[0070] Step 4: A crosslinking solution was prepared. 70 mL of a 0.04 M sulfuric acid solution was taken, and 2 g of the above obtained composite fiber membrane was soaked in the sulfuric acid solution. Then, 0.05 g of glutaraldehyde was further added. After constant temperature soaking at 70°C for 10 h, the fiber membrane was vacuum dried at 75°C for 12 h to obtain a cyclodextrin silver supramolecular assembly structure composite nanofiber membrane with a crosslinked structure.

[0071] Comparative Example 1

[0072] This comparative example provides a preparation method of a PAN nanofiber membrane. The specific steps are as follows: 5 g of polyacrylonitrile with a weight average molecular weight of 10 w was weighed and added to 50 g of N,N-dimethylformamide. A PAN nanofiber membrane was obtained under the same electrospinning conditions as Example 1.

[0073] Figure 3 and Figure 4 are respectively the antibacterial ability comparison diagram and the moisture absorption ability comparison diagram of the composite nanofiber membranes of Examples 1-4 and the PAN nanofiber membrane of Comparative Example 1. It can be seen from the figures that the antibacterial performance and moisture absorption performance of the composite nanofiber membranes prepared in Examples 1-4 are obviously better than those of the PAN nanofiber membrane of Comparative Example 1.

[0074] The foregoing description of the embodiments has been presented for the purpose of illustration and description. It is not intended to be exhaustive or to limit the application to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the application be limited not with this detailed description, but rather by the claims appended hereto.

Claims

1. A method for preparing a high-hygroscopic antibacterial composite nanofiber membrane, characterized in that, The method comprises the following steps: (1) adding silver nitrate solution into the amine cyclodextrin solution, adjusting the pH of the reaction solution with sodium hydroxide solution, controlling the reaction temperature to be 20-100℃, the pH to be 3-14, the stirring speed to be 30-300 r / min, and the reaction time to be 0.5-10 h, washing and centrifuging multiple times after the reaction is completed, the centrifugal speed being 3000-15000 rpm, and the centrifugal time being 10-60 min, to obtain the amine cyclodextrin nanosilver supermolecular assembly structure, wherein: The amine cyclodextrin is obtained by sulfonating cyclodextrin with 4-methyl benzene sulfonyl chloride reagent and then treating with an amine reagent; The concentration of the silver nitrate solution is 0.05-5 mmol / L, and the concentration of the amine cyclodextrin solution is 0.5-10 mmol / L; The amine reagent is selected from one of ethylenediamine, diethylenetriamine and triethylenetetramine; The cyclodextrin is selected from one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin; The concentration of the silver nitrate solution is one of 0.1 mmol / L, 0.2 mmol / L, 0.3 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.6 mmol / L, 0.7 mmol / L, 0.8 mmol / L, 0.9 mmol / L and 1 mmol / L; The concentration of the amine cyclodextrin solution is one of 1 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L and 5 mmol / L; The reaction temperature is one of 50℃, 55℃, 60℃, 65℃ and 70℃; The reaction time is one of 2 h, 3 h, 4 h, 5 h and 6 h; The pH of the reaction solution is one of 5, 6, 7, 8, 9, 10, 11 and 12; The stirring speed is one of 80 r / min, 100 r / min, 120 r / min, 140 r / min and 160 r / min; The centrifugal speed is one of 5000 rpm, 6000 rpm, 7000 rpm, 8000 rpm, 9000 rpm and 10000 rpm; The centrifugal time is one of 15 min, 20 min, 25 min, 30 min, 35 min and 40 min; (2) using an aprotic polar solvent, the amine cyclodextrin nanosilver supermolecular assembly structure obtained in step (1) is prepared into a composite spinning solution together with polyacrylonitrile and polyvinyl alcohol, and an electrospinning process is adopted to prepare a composite nanofiber membrane; The aprotic polar solvent is selected from one of N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide; The weight average molecular weight of the polyacrylonitrile is 5-20 w; The weight average molecular weight of the polyvinyl alcohol is 3-15 w; The concentration of the polyacrylonitrile in the composite spinning solution is 5%-40% by mass; the mass ratio of the polyvinyl alcohol to the polyacrylonitrile is 1:10-1:1; and the mass ratio of the amine cyclodextrin nanosilver to the polyacrylonitrile is 1:50-1:

10. The stirring temperature is 20-60℃; the stirring time is 6-24h; and the stirring speed is 200-800 r / min; The voltage of the electrostatic spinning process of the composite spinning solution is 10-50kV, the fiber receiving distance is 10-35cm, the outflow speed of the spinning solution is 0.1-3mL / h, the spinning needle inner diameter is 0.2-2mm, the spinning temperature is 20-70℃, and the relative humidity is 10%-25%; (3) In a sulfuric acid solution, the composite nanofiber membrane obtained in step (2) is grafted and crosslinked by using a dialdehyde, and after the reaction is completed, vacuum drying is performed to obtain a high-hygroscopic antibacterial composite nanofiber membrane with a crosslinked structure; The concentration of the sulfuric acid solution is 0.01-0.1 M; the dialdehyde is selected from one of propylene glycol, glutaraldehyde, and adipaldehyde; and the addition amount of the dialdehyde is 0.01%-10% of the composite nanofiber membrane by mass; The crosslinking time of the composite nanofiber membrane is 0.5-12h, and the crosslinking temperature is 30-90℃; the vacuum drying temperature is 40-100℃, and the drying time is 0.5-12h.

2. A high-hygroscopic antibacterial composite nanofiber membrane with a crosslinked structure of a cyclodextrin nanosilver supramolecular assembly structure, which is obtained by the preparation method of the high-hygroscopic antibacterial composite nanofiber membrane according to claim 1.

3. Application of the high-hygroscopic antibacterial composite nanofiber membrane according to claim 2 to functional textiles.

Images