Preparation method of anti-ultraviolet / super-hydrophobic multifunctional cashmere fabric

Abstract

The application provides a preparation method of an anti-ultraviolet / super-hydrophobic multifunctional silk cashmere fabric, comprising the following steps: S1, adding polylactic acid powder into dichloromethane to obtain a polylactic acid solution; S2, covering the silk cashmere fabric on a receiving plate, smearing a layer of silk fibroin protein solution on the surface of the silk cashmere fabric, and preparing an electrospun fiber layer on one side of the surface of the silk cashmere fabric on which the silk fibroin protein solution is smeared through electrospinning; S3, adding raspberry-shaped CeO2 / SiO2 composite microspheres into an N, N-dimethylformamide solution, ultrasonic dispersion, then adding polylactic acid and dichloromethane into the above solution, stirring and dissolving to obtain a composite microsphere / polylactic acid precursor solution; and S4, taking the electrospun fiber layer prepared in step S2 as a receiving surface, and performing electrostatic spraying to obtain the anti-ultraviolet / super-hydrophobic multifunctional silk cashmere fabric. Through cooperation of the electrospinning and electrostatic spraying methods, the dispersibility and the bonding strength of nanometer cerium dioxide are improved.

Description

Technical Field

[0001] This invention relates to the field of functional fabrics, specifically to a method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric. Background Technology

[0002] Silk cashmere is a blend of silk and wool, resulting in a soft, thick fabric with excellent breathability, moisture permeability, drape, and comfort, making it widely used in the textile and apparel industry. However, despite these superior properties, silk and wool products still suffer from drawbacks such as wrinkling, yellowing, poor abrasion resistance, fading, difficulty in care, and poor UV and antibacterial properties. Furthermore, the limited variety, low technological content, and low added value of these products significantly restrict their further development. Combining nanomaterials with silk cashmere fabrics can effectively improve these inherent defects, expand their application range, and increase their added value. Numerous studies have shown that using nanomaterials such as titanium dioxide, zinc oxide, graphene, graphene oxide, carbon nanotubes, nano-silver, and nano-gold to treat silk cashmere and its products can endow them with excellent antibacterial, UV-resistant, self-cleaning, anti-yellowing, and conductive properties.

[0003] Ultraviolet (UV) radiation can be divided into three bands based on its wavelength: UVA (315–400 nm), UVB (280–315 nm), and UVC (below 280 nm). Short-wave UV radiation, or UVC, consists of ultraviolet light with wavelengths below 280 nm. Short-wave UV radiation is absorbed by the ozone layer when passing through the stratosphere and cannot reach the Earth's surface. Medium-wave UV radiation, or UVB, consists of ultraviolet light with wavelengths of 280–315 nm. Medium-wave UV radiation has certain physiological effects on human skin. Most of this type of UV radiation is absorbed by the epidermis and cannot penetrate the skin. However, due to its higher energy, it can cause strong photodamage to the skin, leading to vasodilation in the dermis and symptoms such as redness, swelling, and blisters. Prolonged exposure can cause erythema, inflammation, and skin aging; in severe cases, it can lead to skin cancer. Long-wave UV radiation, or UVA, consists of ultraviolet light with wavelengths of 315–400 nm. Long-wave ultraviolet (UV) radiation penetrates clothing and human skin much more strongly than medium-wave ultraviolet (UVB) radiation, reaching deep into the dermis. While UVB radiation does not cause acute skin inflammation, its effects on the skin are slow and cumulative, contributing to skin aging and serious damage. With rising living standards, people are increasingly aware of the harmful effects of UVA and UVB radiation (wavelengths 280-400nm). Therefore, UV-resistant finishing of silk and cashmere plays a crucial role in protecting human health and the silk / wool fibers themselves, leading to a strong market demand for UV-resistant / protective silk and cashmere fabrics.

[0004] Nano-cerium dioxide possesses a unique 4F electron layer structure, exhibiting strong ultraviolet shielding capabilities. Furthermore, due to its large bandgap, it provides a wide shielding range for the ultraviolet band. In addition, cerium dioxide is non-toxic and relatively stable, making it an excellent choice for ultraviolet shielding agents. This project utilizes nano-cerium dioxide layer-by-layer self-assembly technology to endow silk cashmere fabrics with excellent UV resistance, superhydrophobicity, and washability, significantly enhancing the added value and application range of silk cashmere fabrics.

[0005] Nano-cerium dioxide modified textiles mainly adhere to the textile surface through physical adsorption. However, the adhesion of these nano-cerium dioxide particles to the textile surface is poor, and they continuously detach after washing. Using chemical cross-linking agents to increase adhesion can pose potential health risks. Furthermore, nano-cerium dioxide has a huge specific surface area and high surface energy, making it prone to aggregation. Improving the dispersibility of nano-cerium dioxide is also a challenge that needs to be addressed. Summary of the Invention

[0006] The technical problem to be solved: The purpose of this invention is to provide a method for preparing an anti-UV / superhydrophobic multifunctional silk cashmere fabric, which improves the dispersibility and binding strength of nano-cerium dioxide by combining electrospinning and electrostatic spraying methods.

[0007] Technical solution: A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric, comprising the following steps:

[0008] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution;

[0009] S2. Cover the receiving plate with silk cashmere fabric, apply a layer of silk fibroin solution to the surface of the silk cashmere fabric, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning.

[0010] S3. Add the raspberry-type CeO2 / SiO2 composite microspheres to an N,N-dimethylformamide solution and disperse them by ultrasonication. Then add polylactic acid and dichloromethane to the above solution and stir to dissolve them to obtain the composite microsphere / polylactic acid precursor solution.

[0011] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying to obtain UV-resistant / superhydrophobic multifunctional silk cashmere fabric.

[0012] Preferably, the concentration of the polylactic acid solution in step S1 is 12-16 wt%.

[0013] Preferably, in step S2, the electrospinning voltage is 15-18V, the spinning distance is 15-20cm, and the spinning speed is 1.5-2.5mL / h.

[0014] Preferably, the preparation method of the raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps:

[0015] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added, and the mixture was heated under nitrogen protection and refluxed to obtain modified silica.

[0016] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0017] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, then add the succinic anhydride solution dropwise to a silica dispersion, stir to react, and obtain carboxyl-functionalized silica;

[0018] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate and subjected to ultrasonic reaction. Then, NaOH solution is added dropwise to the reaction solution while stirring to obtain composite microspheres.

[0019] S15. The composite microspheres were calcined to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0020] Preferably, in step S3, the mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide, and dichloromethane in the composite microsphere / polylactic acid precursor solution is 0.5-1:2-3:15:15.

[0021] Preferably, in step S4, the voltage is 16-18V, the receiving distance is 18-20cm, and the injection speed is 2-2.5mL / h.

[0022] Preferably, in step S11, the mass ratio of micron-sized silica to 3-aminopropyltriethylsilane is 1:5-7, the reflux reaction temperature is 100-110°C, and the time is 15-30 h.

[0023] Preferably, the mass ratio of succinic anhydride to micron-sized silica is 1-1.5:1.

[0024] Preferably, in step S14, the mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1-2, the concentration of cerium nitrate is 0.05-0.15 mol / L, and the stirring speed is 500-700 r / min.

[0025] Preferably, the calcination temperature in step S15 is 400-500℃ and the time is 20-30 min.

[0026] Beneficial effects: The preparation method of the present invention has the following advantages:

[0027] This invention first uses electrospinning to prepare a layer of PLA nanofibers with nanometer diameters on the surface of silk cashmere fabric. Then, by electrostatic spraying, a layer of raspberry-type CeO2 / SiO2 composite microspheres with micron structure is attached to the surface of the electrospinned film. The combination of nanofibers and micron composite microspheres forms a dual-scale rough structure combining micro and nano, which can obtain a superhydrophobic coating with a static contact angle greater than 150°, overcoming the shortcomings of existing superhydrophobic construction methods such as complexity, high cost and poor adhesion.

[0028] In this invention, positively charged Ce ions and negatively charged SiO2 are combined by electrostatic adsorption to form composite microspheres. Electrostatic spraying is then used to ensure that the CeO2 / SiO2 composite microspheres are evenly distributed on the surface of the silk cashmere fabric, resulting in a UV-resistant / superhydrophobic multifunctional silk cashmere fabric. Detailed Implementation

[0029] The present invention will be further described below with reference to embodiments. These embodiments are illustrative of the present invention, but the present invention is not limited to these embodiments:

[0030] Example 1

[0031] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0032] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 12wt%;

[0033] S2. Cover the receiving plate with silk cashmere fabric, apply a layer of silk fibroin solution to the surface of the silk cashmere fabric, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 15V, the spinning distance is 20cm, and the spinning speed is 1.5mL / h.

[0034] S3. Raspberry-type CeO2 / SiO2 composite microspheres were added to an N,N-dimethylformamide solution and ultrasonically dispersed. Then, polylactic acid and dichloromethane were added to the above solution. The mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution was 0.5:2:15:15. The solution was stirred and dissolved to obtain the composite microsphere / polylactic acid precursor solution.

[0035] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 16V, a receiving distance of 18cm, and an injection speed of 2mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0036] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps:

[0037] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:5. The mixture was heated under nitrogen protection and refluxed at 110°C for 15 hours to obtain modified silica.

[0038] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0039] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0040] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1, and the concentration of cerium nitrate is 0.05 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 500 r / min to obtain composite microspheres.

[0041] S15. The composite microspheres were calcined at 500℃ for 20 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0042] Example 2

[0043] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0044] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 16wt%;

[0045] S2. Cover the receiving plate with silk cashmere fabric, apply a layer of silk fibroin solution to the surface of the silk cashmere fabric, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 18V, the spinning distance is 15cm, and the spinning speed is 2.5mL / h.

[0046] S3. Add raspberry-type CeO2 / SiO2 composite microspheres to an N,N-dimethylformamide solution and disperse by ultrasonication. Then add polylactic acid and dichloromethane to the above solution. The mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution is 1:3:15:15. Stir to dissolve and obtain the composite microsphere / polylactic acid precursor solution.

[0047] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 18V, a receiving distance of 20cm, and an injection speed of 2.5mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0048] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps:

[0049] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:7. The mixture was heated under nitrogen protection and refluxed at 100°C for 30 hours to obtain modified silica.

[0050] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0051] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1.5:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0052] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 5:1, and the concentration of cerium nitrate is 0.15 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 700 r / min to obtain composite microspheres.

[0053] S15. The composite microspheres were calcined at 400℃ for 30 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0054] Example 3

[0055] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0056] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 14wt%;

[0057] S2. Cover the receiving plate with silk cashmere fabric, coat the surface of the silk cashmere fabric with a layer of silk fibroin solution, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 16V, the spinning distance is 15cm, and the spinning speed is 1.8mL / h.

[0058] S3. Raspberry-type CeO2 / SiO2 composite microspheres were added to an N,N-dimethylformamide solution and ultrasonically dispersed. Then, polylactic acid and dichloromethane were added to the above solution. The mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution was 0.8:2.2:15:15. The solution was stirred and dissolved to obtain the composite microsphere / polylactic acid precursor solution.

[0059] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 16V, a receiving distance of 20cm, and an injection speed of 2.5mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0060] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps:

[0061] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:6. The mixture was heated under nitrogen protection and refluxed at 110°C for 25 hours to obtain modified silica.

[0062] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0063] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1.2:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0064] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1.7, and the concentration of cerium nitrate is 0.12 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 550 r / min to obtain composite microspheres.

[0065] S15. The composite microspheres were calcined at 480℃ for 20 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0066] Example 4

[0067] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0068] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 15wt%;

[0069] S2. Cover the receiving plate with silk cashmere fabric, coat the surface of the silk cashmere fabric with a layer of silk fibroin solution, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 18V, the spinning distance is 18cm, and the spinning speed is 2.2mL / h.

[0070] S3. Raspberry-type CeO2 / SiO2 composite microspheres were added to an N,N-dimethylformamide solution and ultrasonically dispersed. Then, polylactic acid and dichloromethane were added to the above solution. The mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution was 1:2.7:15:15. The solution was stirred and dissolved to obtain the composite microsphere / polylactic acid precursor solution.

[0071] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 18V, a receiving distance of 18cm, and an injection speed of 2mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0072] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps:

[0073] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:7. The mixture was heated under nitrogen protection and refluxed at 105°C for 20 hours to obtain modified silica.

[0074] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0075] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1.4:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0076] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1.4, and the concentration of cerium nitrate is 0.08 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 650 r / min to obtain composite microspheres.

[0077] S15. The composite microspheres were calcined at 450℃ for 30 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0078] Example 5

[0079] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0080] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 15wt%;

[0081] S2. Cover the receiving plate with silk cashmere fabric, apply a layer of silk fibroin solution to the surface of the silk cashmere fabric, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 18V, the spinning distance is 16cm, and the spinning speed is 2mL / h.

[0082] S3. Raspberry-type CeO2 / SiO2 composite microspheres were added to an N,N-dimethylformamide solution and ultrasonically dispersed. Then, polylactic acid and dichloromethane were added to the above solution. The mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution was 1:2.5:15:15. The solution was stirred and dissolved to obtain the composite microsphere / polylactic acid precursor solution.

[0083] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 18V, a receiving distance of 20cm, and an injection speed of 2mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0084] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps:

[0085] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:6.5. The mixture was heated under nitrogen protection and refluxed at 100°C for 20 hours to obtain modified silica.

[0086] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0087] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1.3:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0088] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1.5, and the concentration of cerium nitrate is 0.1 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 600 r / min to obtain composite microspheres.

[0089] S15. The composite microspheres were calcined at 460℃ for 25 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0090] Comparative Example 1

[0091] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0092] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 14wt%;

[0093] S2. Cover the receiving plate with silk cashmere fabric, coat the surface of the silk cashmere fabric with a layer of silk fibroin solution, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 16V, the spinning distance is 15cm, and the spinning speed is 1.8mL / h.

[0094] S3. Add SiO2 microspheres to an N,N-dimethylformamide solution and disperse by ultrasonication. Then add polylactic acid and dichloromethane to the above solution. The mass ratio of SiO2 microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution is 0.8:2.2:15:15. Stir to dissolve and obtain the composite microsphere / polylactic acid precursor solution.

[0095] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 16V, a receiving distance of 20cm, and an injection speed of 2.5mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0096] Comparative Example 2

[0097] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0098] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 15wt%;

[0099] S2. Add raspberry-type CeO2 / SiO2 composite microspheres to the polylactic acid solution prepared in step S1. The content of raspberry-type CeO2 / SiO2 composite microspheres in the polylactic acid solution is 3.6 wt%, and an electrospinning solution is obtained.

[0100] S3. Cover the receiving plate with silk cashmere fabric, coat the surface of the silk cashmere fabric with a layer of silk fibroin solution, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 20V, the spinning distance is 20cm, and the spinning speed is 3mL / h to obtain an anti-ultraviolet / superhydrophobic multifunctional silk cashmere fabric.

[0101] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S2 includes the following steps:

[0102] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:6.5. The mixture was heated under nitrogen protection and refluxed at 100°C for 20 hours to obtain modified silica.

[0103] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0104] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1.3:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0105] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1.5, and the concentration of cerium nitrate is 0.1 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 600 r / min to obtain composite microspheres.

[0106] S15. The composite microspheres were calcined at 460℃ for 25 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0107] Comparative Example 3

[0108] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0109] S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution with a concentration of 15wt%;

[0110] S2. Cover the receiving plate with silk cashmere fabric, coat the surface of the silk cashmere fabric with a layer of silk fibroin solution, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. The electrospinning voltage is 18V, the spinning distance is 18cm, and the spinning speed is 2.2mL / h.

[0111] S3. Add CeO2 particles to N,N-dimethylformamide solution and disperse by ultrasonication. Then add polylactic acid and dichloromethane to the above solution. The mass ratio of CeO2 particles, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution is 1:2.7:15:15. Stir to dissolve and obtain composite microsphere / polylactic acid precursor solution.

[0112] S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, perform electrostatic spraying at a voltage of 18V, a receiving distance of 18cm, and an injection speed of 2mL / h to obtain an anti-UV / superhydrophobic multifunctional silk cashmere fabric.

[0113] Comparative Example 4

[0114] A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric includes the following steps:

[0115] S1. Raspberry-type CeO2 / SiO2 composite microspheres were added to an N,N-dimethylformamide solution and ultrasonically dispersed. Then, polylactic acid and dichloromethane were added to the above solution. The mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide and dichloromethane in the composite microsphere / polylactic acid precursor solution was 1:2.5:15:15. The solution was stirred and dissolved to obtain the composite microsphere / polylactic acid precursor solution.

[0116] S2. Using a silk cashmere fabric coated with silk fibroin solution as the receiving surface, electrostatic spraying is performed at a voltage of 18V, a receiving distance of 20cm, and an injection speed of 2mL / h to obtain a UV-resistant / superhydrophobic multifunctional silk cashmere fabric.

[0117] The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S1 includes the following steps:

[0118] S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added. The mass ratio of micron-sized silica to 3-aminopropyltriethylsilane was 1:6.5. The mixture was heated under nitrogen protection and refluxed at 100°C for 20 hours to obtain modified silica.

[0119] S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion;

[0120] S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, and then add the succinic anhydride solution dropwise to the silica dispersion. The mass ratio of succinic anhydride to micron-sized silica is 1.3:1. Stir the reaction to obtain carboxyl-functionalized silica.

[0121] S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate. The mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1.5, and the concentration of cerium nitrate is 0.1 mol / L. The reaction is carried out by sonication, and then NaOH solution is added dropwise to the reaction solution while stirring at a speed of 600 r / min to obtain composite microspheres.

[0122] S15. The composite microspheres were calcined at 460℃ for 25 min to obtain raspberry-type CeO2 / SiO2 composite microspheres.

[0123] Performance testing: Hydrophobicity was characterized by measuring the contact angle of a water droplet on the fabric surface using a contact angle meter (10 μL); hydrophobicity was measured again after 20 washes.

[0124] Ultraviolet transmittance was measured using a spectrophotometer.

[0125] Contact angle / ° Contact angle after 20 washes / ° UVA / % UVB / % UVC / % Example 1 155.2 153.6 4.85 4.33 2.69 Example 2 156.1 154.0 5.12 4.45 2.82 Example 3 154.5 152.6 4.69 4.02 3.01 Example 4 156.4 153.7 6.01 4.69 2.96 Example 5 155.6 152.4 5.55 5.02 3.02 Comparative Example 1 152.1 145.6 14.00 7.25 6.95 Comparative Example 2 145.6 144.8 5.69 4.62 2.95 Comparative Example 3 143.4 143.2 8.25 6.59 5.63 Comparative Example 4 146.8 144.9 6.12 5.12 3.21

[0126] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing a UV-resistant / superhydrophobic multifunctional silk cashmere fabric, characterized in that, Includes the following steps: S1. Polylactic acid powder is added to dichloromethane to obtain a polylactic acid solution; S2. Cover the receiving plate with silk cashmere fabric, apply a layer of silk fibroin solution to the surface of the silk cashmere fabric, and prepare an electrospun fiber layer on the side of the silk cashmere fabric coated with silk fibroin solution by electrospinning. S3. Add the raspberry-type CeO2 / SiO2 composite microspheres to an N,N-dimethylformamide solution and disperse them by ultrasonication. Then add polylactic acid and dichloromethane to the above solution and stir to dissolve them to obtain the composite microsphere / polylactic acid precursor solution. S4. Using the electrospun fiber layer prepared in step S2 as the receiving surface, electrostatic spraying is performed to obtain a UV-resistant / superhydrophobic multifunctional silk cashmere fabric; The preparation method of raspberry-type CeO2 / SiO2 composite microspheres in step S3 includes the following steps: S11. Micron-sized silica was added to toluene and stirred until homogeneous. Then, 3-aminopropyltriethylsilane was added, and the mixture was heated under nitrogen protection and refluxed to obtain modified silica. S12. Add the modified silica to N,N-dimethylformamide and stir to disperse evenly to obtain a silica dispersion; S13. Add succinic anhydride to N,N-dimethylformamide, stir to dissolve, then add the succinic anhydride solution dropwise to a silica dispersion, stir to react, and obtain carboxyl-functionalized silica; S14. The carboxyl-functionalized silica prepared in step S13 is added to cerium nitrate and subjected to ultrasonic reaction. Then, NaOH solution is added dropwise to the reaction solution while stirring to obtain composite microspheres. S15. The composite microspheres were calcined to obtain raspberry-type CeO2 / SiO2 composite microspheres.

2. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: The concentration of the polylactic acid solution in step S1 is 12-16 wt%.

3. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: In step S2, the electrospinning voltage is 15-18V, the spinning distance is 15-20cm, and the spinning speed is 1.5-2.5mL / h.

4. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: In step S3, the mass ratio of raspberry-type CeO2 / SiO2 composite microspheres, polylactic acid, N,N-dimethylformamide, and dichloromethane in the composite microsphere / polylactic acid precursor solution is 0.5-1:2-3:15:

15.

5. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: In step S4, the voltage is 16-18V, the receiving distance is 18-20cm, and the injection speed is 2-2.5mL / h.

6. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: In step S11, the mass ratio of micron-sized silica to 3-aminopropyltriethylsilane is 1:5-7, the reflux reaction temperature is 100-110℃, and the time is 15-30h.

7. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: The mass ratio of succinic anhydride to micron-sized silica is 1-1.5:

1.

8. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: In step S14, the mass ratio of carboxyl-functionalized silica to cerium nitrate is 10:1-2, the concentration of cerium nitrate is 0.05-0.15 mol / L, and the stirring speed is 500-700 r / min.

9. The method for preparing the UV-resistant / superhydrophobic multifunctional silk cashmere fabric according to claim 1, characterized in that: In step S15, the calcination temperature is 400-500℃ and the time is 20-30 minutes.