Antibacterial and ultraviolet resistant biol / zno / cs composite material and preparation method thereof

Abstract

The present application relates to a kind of for antibacterial anti-ultraviolet BiOI / ZnO / CS composite material and preparation method thereof, preparation method includes: ZnO / chitosan composite material is dispersed in ethylene glycol, after ultrasonic, it is added to the mixed solution of Bi (NO3) 3 5H2O and polyvinylpyrrolidone dissolved in ethylene glycol, obtain solution 1, KI is completely dissolved in ethylene glycol, obtain solution 2, by syringe slowly drop solution 2 into solution 1 under severe stirring, continue stirring 2-3h, mixed liquid is transferred to the stainless steel autoclave lined with Teflon, at 140-160 ℃ reaction 12-14h, cooling to room temperature, centrifugal, and with deionized water and ethanol wash, dry overnight, obtain BiOI / ZnO / chitosan composite material.The composite material of the present application improves the antibacterial, anti-ultraviolet and hydrophobic properties of fabric.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photocatalytic material synthesis, and particularly relates to a BiOI / ZnO / CS composite material, a preparation method and application thereof. BACKGROUND

[0002] Textiles are conducive to the adhesion of microorganisms due to their porous object shape and the chemical structure of polymer polymers, becoming a good parasite for the survival and reproduction of microorganisms. Textiles have no inhibition and killing function on bacteria, and therefore, textiles are considered to be a good carrier for bacteria, fungi and other microorganisms. The metabolic products of microorganisms not only have irritating odor, but also have harmful stimulation to human skin, causing diseases, and a large number of breeding of microorganisms can also seriously reduce the performance of textiles, causing mildew, embrittlement and even deterioration, affecting use. Linen fabric is the first choice for summer clothing fabric due to its moisture absorption and air permeability, but its ultraviolet shielding ability is weak and the antibacterial performance is not enough, so the development and application of multifunctional finishing agents such as antibacterial and ultraviolet resistant on textiles have become a hot research angle. SUMMARY

[0003] The application aims to at least solve one of the technical problems in the related art, and for this purpose, the application embodiment provides a new composite material generated by chelation of ZnO and BiOI with amino hydroxyl groups on chitosan (CS).

[0004] The application embodiment further provides a preparation method of the composite material.

[0005] The application embodiment further provides application of the composite material in a linen fabric finishing process.

[0006] The technical solution adopted by the application embodiment is as follows:

[0007] The application embodiment provides a preparation method of a BiOI / ZnO / chitosan composite material, including the following steps:

[0008] S1: dissolve chitosan in an acetic acid solution, add zinc acetate dihydrate, and stir at room temperature until dissolved;

[0009] S2: in a reaction kettle with a water bath temperature of 60-70 DEG C, add the solution of step S1, drop NaOH solution to pH = 9-10, stir for 3-4 h, cool to room temperature after reaction, wash with deionized water and ethanol for several times until neutral, centrifuge; dry at 70-80 DEG C overnight, grind into powder, and obtain ZnO / chitosan composite material;

[0010] S3: ZnO / chitosan composite material is dispersed in ethylene glycol, after ultrasonic treatment for 30-60 min, it is added into a mixed solution of Bi(NO3)3.5H2O and polyvinylpyrrolidone dissolved in ethylene glycol to obtain solution 1, KI is completely dissolved in ethylene glycol to obtain solution 2, solution 2 is slowly added into solution 1 under vigorous stirring through a syringe, stirring is continued for 2-3 h, the mixture is transferred into a Teflon-lined stainless steel autoclave, reaction is carried out at 140-160℃ for 12-14 h, cooling is carried out to room temperature, centrifugation is carried out, and washing is carried out with deionized water and ethanol, drying is carried out at 70-80℃ overnight to obtain a BiOI / ZnO / chitosan composite material.

[0011] In some embodiments, the degree of deacetylation of the chitosan is ≥95%, the viscosity is 100-200 mPa·s, and the molecular weight is 120-260,000.

[0012] In some embodiments, in step S1, the concentration of the acetic acid solution is 1%.

[0013] In some embodiments, in step S1, the molar ratio of chitosan to zinc acetate dihydrate is 1:1.

[0014] In some embodiments, in step S2, the concentration of the NaOH solution is 1 mol / L.

[0015] In some embodiments, in step S3, the mass ratio of ZnO / chitosan composite material to Bi(NO3)3.5H2O is (3.2-16):1. Preferably, the mass ratio is (3.2-8):1; more preferably, the mass ratio is (3.2-5.3):1; more preferably, the mass ratio is 4:1.

[0016] In some embodiments, in step S3, the molar ratio of KI to Bi(NO3)3.5H2O is 1:1.

[0017] In some embodiments, in step S3, the mass ratio of Bi(NO3)3.5H2O to polyvinylpyrrolidone is (4.5-4.6):1.

[0018] The application also provides a BiOI / ZnO / chitosan composite material prepared by the above preparation method.

[0019] The application also provides application of the above BiOI / ZnO / chitosan composite material in textile antibacterial and ultraviolet resistant finishing.

[0020] In some embodiments of the application, the textile is linen fabric, and the BiOI / ZnO / chitosan composite material is mixed with distilled water under ultrasonic treatment to serve as a fabric finishing liquid, and the bath ratio is 30:1.

[0021] The embodiments of the present invention have the following advantages and beneficial effects:

[0022] (1) The composite material of the present invention is obtained by modifying chitosan with ZnO and BiOI. Chitosan has abundant hydroxyl and amino groups, which have a strong chelating effect on metals or metal oxides. The band gap of ZnO is about 3.2 eV and the band gap of BiOI is about 1.8 eV. Based on the band gap compatibility of ZnO and BiOI, chitosan works synergistically to enhance antibacterial and UV protection, thereby improving the antibacterial, UV protection and hydrophobic properties of the composite material of the present invention and improving the antibacterial, UV protection and hydrophobic properties of the fabric.

[0023] (2) The preparation method of the composite material in the embodiments of the present invention is simple, the raw materials are readily available, and it has good prospects for industrial production. Attached Figure Description

[0024] Figure 1 Infrared spectra of CS, ZnO, ZnO / CS, BiOI, and 20% BiOI / ZnO / CS.

[0025] Figure 2 Surface morphology analysis diagrams of flax fabrics before and after finishing, including CS, ZnO / CS, BiOI, 20% BiOI / ZnO / CS.

[0026] Figure 3 EDS analysis diagram of unfinished linen fabric;

[0027] Figure 4 EDS analysis diagram of flax fabric treated with 20% BiOI / ZnO / CS;

[0028] Figure 5 The graph shows the antibacterial rate of flax fabrics before and after treatment with 20% BiOI / ZnO / CS. Detailed Implementation

[0029] The present invention will be further described below with reference to embodiments. It should be understood that these embodiments are for illustrative purposes only and do not limit the scope of protection of the present invention.

[0030] Chitosan (CS) is a representative class of animal-derived natural antibacterial agents. It possesses good biocompatibility and exhibits effective inhibition against most bacteria, making it a green and environmentally friendly antibacterial material with wide applications in textiles, medicine, and environmental protection. However, chitosan's antibacterial activity is limited. Therefore, modification of chitosan is crucial for enhancing its antibacterial properties. The numerous amino and hydroxyl groups on chitosan can be utilized to chelate with metal ions, further strengthening its antibacterial performance.

[0031] ZnO is a common wide band gap semiconductor metal oxide, which has good biocompatibility, thermal stability and chemical stability. It is an inorganic antibacterial agent, which has broad-spectrum antibacterial performance and is non-toxic, so it becomes a research hotspot in the field of textile antibacterial. At the same time, ZnO has good ultraviolet shielding effect. BiOI has the narrowest band gap among bismuth-containing semiconductors, about 1.8eV, and has excellent visible light absorption performance, but its application is affected by high photo-induced electron-hole recombination rate and low electron transfer ability. These defects make it a suitable material to form a composition with ZnO. Therefore, the natural antibacterial agent chitosan is combined with inorganic antibacterial agents ZnO and BiOI and applied to textiles in the embodiments of the present application, and good antibacterial and ultraviolet resistance is given.

[0032] Therefore, the BiOI / ZnO / chitosan composite material is completed by chelation of ZnO and BiOI with the hydroxyl and amino groups on the chitosan, and the specific steps are shown in Examples 1-5.

[0033] The chitosan used in Examples 1-5 has a degree of deacetylation of 95% or more and a viscosity of 100-200 mPa·s.

[0034] In the embodiments and comparative examples of the present application,

[0035] The groups of the samples are characterized by using a Spectrum 100 type Fourier transform infrared spectrometer (FTIR) (American PE company), and the KBr pressing method is used for testing, and the wave number range is 4000-520 cm -1 .

[0036] The surface of the sample is observed by using an S-3400 type scanning electron microscope (SEM) (Hitachi Ltd. of Japan).

[0037] The element distribution of the sample is tested by using an X-Max 50 energy spectrometer.

[0038] The antibacterial performance of flax fabric on Staphylococcus aureus and Escherichia coli before and after treatment is detected according to the relevant provisions of GB / T20944 Part 3 Article 129 oscillation method. The flax fabric before and after treatment is cut into a circular piece with a diameter of 6mm by using a punch, and then sterilized. The sterilized fabric is placed in a sterile culture plate and 1mL of bacterial suspension is added for co-culture for 30min. The culture plate is placed in a photocatalytic reactor and irradiated for 2h by using a 210W xenon lamp. Then the culture plate is placed in a shaking bed at 37℃, 150r / min and shaken for 24h. After shaking, 20uL is uniformly coated on the solid culture medium, and incubated in a constant temperature incubator at 37℃ for 24h. The antibacterial rate is calculated according to the following formula.

[0039]

[0040] wherein Y is the antibacterial rate; W b is the number of viable bacteria after the original cloth sample is shaken for 24 hours; W a is the number of viable bacteria after the finished fabric is shaken for 24 hours. Wherein the antibacterial rate is greater than or equal to 90%, it indicates that the sample has antibacterial effect.

[0041] YG(B)912E type textile anti-ultraviolet performance tester (UPF) is used to test the anti-ultraviolet performance of different samples on linen fabric, and the same fabric is tested three times to take the average value.

[0042] JY-82B type contact angle tester (Chengde Dingsheng Test Machine Detection Equipment Co., Ltd.) is used to measure the static water contact angle of the finished fabric, and 3 different positions of the same fabric are selected for measurement, and the average value is taken.

[0043] The crease recovery angle is tested according to ISO 2313-1972 "Determination of the crease recovery of a horizontal specimen of a textile fabric by means of the angle of recovery" method and GB / T 3819-1997 "Determination of the crease recovery of a horizontal specimen of a textile fabric by means of the angle of recovery" method.

[0044] Determination is carried out according to ISO 13934-1:1999 "Textiles- Determination of the tensile properties of fabrics-Part 1: maximum force and elongation at break strip method" and GB / T 3923.1-2013 "Textiles- Determination of the tensile properties of fabrics-Part 1: maximum force and elongation at break strip method".

[0045] Example 1: Preparation of 5% BiOI / ZnO / CS composite material.

[0046] 1.36g of ZnO / CS composite material (preparation method see comparative example 3) is ultrasonically dispersed in 20mL of ethylene glycol for 30min to obtain a ZnO-CS dispersion liquid, 0.085g of Bi(NO3)3·5H2O and 0.0185g of polyvinylpyrrolidone are dissolved in 10mL of ethylene glycol, and the ZnO-CS dispersion liquid is added to obtain solution 1. 0.02905g of KI is completely dissolved in ethylene glycol to obtain solution 2, and solution 2 is slowly added to solution 1 by syringe under vigorous stirring, and stirring is continued for 2h, the mixture is transferred to a Teflon-lined stainless steel autoclave, reacted at 140℃ for 12h, cooled to room temperature, centrifuged, and washed with deionized water and ethanol, dried at 70℃ overnight to obtain 5% BiOI / ZnO / chitosan composite material.

[0047] Example 2: Preparation of 10% BiOI / ZnO / CS composite material.

[0048] Take 1.36 g of ZnO / CS composite material (see Example 3 for preparation method), ultrasonic dispersion in 20 mL of ethylene glycol for 30 min to obtain ZnO-CS dispersion, then take 0.17 g of Bi(NO3)3·5H2O and 0.0375 g of polyvinylpyrrolidone and dissolve them in 10 mL of ethylene glycol, and then add the ZnO-CS dispersion to obtain solution 1. Take 0.0581 g of KI and completely dissolve it in ethylene glycol to obtain solution 2. Slowly add solution 2 to solution 1 by syringe under vigorous stirring, continue stirring for 2 h, transfer the mixture to a Teflon-lined stainless steel autoclave, react at 140°C for 12 h, cool to room temperature, centrifuge, and wash with deionized water and ethanol, and dry at 70°C overnight to obtain a 10% BiOI / ZnO / chitosan composite material.

[0049] Example 3: Preparation of 15% BiOI / ZnO / CS composite material.

[0050] Take 1.36 g of ZnO / CS composite material (see Example 3 for preparation method), ultrasonic dispersion in 20 mL of ethylene glycol for 30 min to obtain ZnO-CS dispersion, then take 0.17 g of Bi(NO3)3·5H2O and 0.0375 g of polyvinylpyrrolidone and dissolve them in 10 mL of ethylene glycol, and then add the ZnO-CS dispersion to obtain solution 1. Take 0.0581 g of KI and completely dissolve it in ethylene glycol to obtain solution 2. Slowly add solution 2 to solution 1 by syringe under vigorous stirring, continue stirring for 2 h, transfer the mixture to a Teflon-lined stainless steel autoclave, react at 140°C for 12 h, cool to room temperature, centrifuge, and wash with deionized water and ethanol, and dry at 70°C overnight to obtain a 10% BiOI / ZnO / chitosan composite material.

[0051] Example 4: Preparation of 20% BiOI / ZnO / CS composite material.

[0052] Take 1.36 g of ZnO / CS composite material (see Example 3 for preparation method), ultrasonic dispersion in 20 mL of ethylene glycol for 30 min to obtain ZnO-CS dispersion, then take 0.17 g of Bi(NO3)3·5H2O and 0.0375 g of polyvinylpyrrolidone and dissolve them in 10 mL of ethylene glycol, and then add the ZnO-CS dispersion to obtain solution 1. Take 0.0581 g of KI and completely dissolve it in ethylene glycol to obtain solution 2. Slowly add solution 2 to solution 1 by syringe under vigorous stirring, continue stirring for 2 h, transfer the mixture to a Teflon-lined stainless steel autoclave, react at 140°C for 12 h, cool to room temperature, centrifuge, and wash with deionized water and ethanol, and dry at 70°C overnight to obtain a 10% BiOI / ZnO / chitosan composite material.

[0053] Example 5: Preparation of 25% BiOI / ZnO / CS composite.

[0054] Take 1.36 g of ZnO / CS composite (preparation method see Comparative Example 3), ultrasonic dispersion in 20 mL of ethylene glycol for 30 min to obtain a ZnO-CS dispersion solution, then take 0.425 g of Bi(NO3)3·5H2O and 0.0925 g of polyvinylpyrrolidone and dissolve them in 10 mL of ethylene glycol, and then add the ZnO-CS dispersion solution to obtain solution 1. Take 0.14525 g of KI and completely dissolve it in 10 mL of ethylene glycol to obtain solution 2. Slowly drop solution 2 into solution 1 through a syringe under vigorous stirring, and continue stirring for 2 h. Transfer the mixed solution to a Teflon-lined stainless steel autoclave, and react at 140°C for 12 h. Cool to room temperature, centrifuge, and wash with deionized water and ethanol, and dry at 70°C overnight to obtain a 25% BiOI / ZnO / chitosan composite.

[0055] Comparative Example 1: Chitosan (CS) (CS, degree of deacetylation ≥95%, viscosity 100-200 mpa·s), purchased from Shanghai Maikelin Biochemical Technology Co., Ltd.

[0056] Comparative Example 2: ZnO, purchased from Tianjin Kermel Chemical Reagent Co., Ltd.

[0057] Comparative Example 3: ZnO / CS.

[0058] Weigh chitosan and dissolve it in 1% acetic acid, then add an equimolar amount of zinc acetate dihydrate, and fully dissolve it at room temperature under magnetic stirring. In a reaction kettle with a water bath temperature of 60°C, add the above mixed solution, and drop NaOH to adjust the pH to 10. Stir for 4 h, and then cool to room temperature. Wash with deionized water and anhydrous ethanol until neutral, centrifuge, and dry at 70°C overnight. Grind into powder to obtain a ZnO / CS composite.

[0059] Comparative Example 4: BiOI.

[0060] Weigh 2.8 mmol of Bi(NO3)3·5H2O and 0.15 g of polyvinylpyrrolidone (PVP), and fully dissolve them in 30 mL of ethylene glycol under magnetic stirring to obtain solution A. Weigh 2.8 mmol of KI and completely dissolve it in 20 mL of ethylene glycol to obtain solution B. Slowly drop solution B into solution A through a syringe under vigorous stirring, and continue stirring for 2 h. Transfer the mixed solution to a Teflon-lined stainless steel high-pressure reaction kettle, and place it in a 140°C oven. After 12 h of incubation, take it out, cool to room temperature, centrifuge, and wash with deionized water and ethanol several times. Dry at 70°C overnight to obtain BiOI nanoparticles.

[0061] Application Example

[0062] The BiOI / ZnO / chitosan composite material of the embodiment of the present application is applied to the fabric.

[0063] Take a piece of linen and weigh it.

[0064] Place the linen in the prepared finishing liquid (BiOI / ZnO / chitosan composite material and distilled water are ultrasonically mixed, 30% owf.), with a bath ratio of 30:1, and perform two dips and two rolls.

[0065] Place the finished fabric in an oven, dry it at 75°C for 5 min to remove water, and then bake it at 95°C for 10 min.

[0066] Application Comparative Example 1

[0067] A method for finishing linen fabric with chitosan, comprising the following steps:

[0068] Take a piece of linen and weigh it.

[0069] Dissolve chitosan in 1% acetic acid solution to prepare a chitosan solution.

[0070] Place the linen in the prepared finishing liquid, and perform two dips and two rolls.

[0071] Place the finished fabric in an oven, dry it at 75°C for 5 min to remove water, and then bake it at 95°C for 10 min to obtain chitosan-finished linen fabric.

[0072] Application Comparative Example 2

[0073] A method for preparing ZnO-finished linen fabric, comprising the following steps:

[0074] Take a piece of linen and weigh it.

[0075] Prepare a ZnO suspension (30% owf.) by mixing ZnO (purchased from Kermel Chemical Reagent Co., Ltd.) with distilled water, with a bath ratio of 30:1.

[0076] Place the linen in the prepared finishing liquid, and perform two dips and two rolls.

[0077] Place the finished fabric in an oven, dry it at 75°C for 5 min to remove water, and then bake it at 95°C for 10 min to obtain ZnO-finished linen fabric.

[0078] Application Comparative Example 3

[0079] A method for preparing ZnO / CS-finished linen fabric, comprising the following steps:

[0080] Take a piece of linen and weigh it.

[0081] ZnO / CS was configured into ZnO / CS suspension (30% owf.) with bath ratio of 30:1.

[0082] The linen was placed in the prepared finishing liquor with two dips and two nips.

[0083] The finished fabric was placed in an oven to dry at 75℃ for 5 min to remove water, and then cured at 95℃ for 10 min to obtain ZnO / CS finished linen fabric.

[0084] Example 4

[0085] A preparation method of BiOI finished linen fabric, comprising the following steps:

[0086] Take a piece of linen and weigh it.

[0087] BiOI was configured into BiOI suspension (30% owf.) with distilled water, with a bath ratio of 30:1.

[0088] The linen was placed in the prepared finishing liquor with two dips and two nips.

[0089] The finished fabric was placed in an oven to dry at 75℃ for 5 min to remove water, and then cured at 95℃ for 10 min to obtain BiOI finished linen fabric.

[0090] Structural characterization

[0091] Figure 1 The infrared spectra of CS, ZnO, ZnO / CS, BiOI, and 20% BiOI / ZnO / CS. The stretching vibration peaks in the range of 3000-3600 cm -1 correspond to O-H and N-H bonds on the CS chain, and the stretching vibration peaks in the range of 1650 cm -1 correspond to the bending vibration of N-H bonds in the CS amide group. In the range of 1000-1200 cm -1 , the asymmetric stretching vibration of CS C-O-C glycosidic bond and the bending vibration of C-N bond appear. In the ZnO / CS sample, a new absorption band of about 500 cm -1 corresponds to Zn-O, indicating that chitosan and ZnO are successfully compounded. In BiOI, the stretching vibration peaks in the range of 400-800 cm -1 correspond to Bi-O, including the asymmetric stretching vibration of Bi-O at 774 cm -1 . The 20% BiOI / ZnO / CS composite material not only has the characteristic peaks of CS, but also has the characteristic peaks of ZnO and BiOI, proving that BiOI and ZnO / CS are successfully compounded.

[0092] SEM

[0093] Figure 2 Figure 1 is the surface morphology analysis diagram of CS, ZnO / CS, BiOI, 20% BiOI / ZnO / CS and linen fabric before and after finishing. From figure 1(a), it can be seen that the surface of CS is smooth. From figure 1(b), it can be seen that after CS is compounded with ZnO, the surface becomes rough and has tiny spherical substances, which indicates that ZnO is successfully compounded with CS. From figure 1(c) and 1(d), it can be seen that BiOI presents uniform spheres, and in BiOI / ZnO / CS, BiOI is attached to the surface of ZnO / CS and connected together through coordination bond. From figure 1(e) and 1(f), it can be seen that the surface of linen fabric is smooth before finishing, while after finishing with 20% BiOI / ZnO / CS, the surface of linen fabric is rough, and the composite material is filled between fibers, forming a strip and uniformly distributed on the surface of linen fabric, which indicates that BiOI / ZnO / CS is successfully finished on the linen fabric. Figure 2 Figure 2 Figure 2 Figure 2

[0094] EDS analysis

[0095] Table 1 is the element distribution mass percentage of linen fabric before and after finishing, Figure 3 Figure 2 is the EDS analysis diagram of linen fabric before finishing, Figure 4 Figure 3 is the EDS analysis diagram of linen fabric after finishing. From table 1, it can be seen that the linen fabric before finishing only contains C and O elements, in which the content of C element is 50.47% and the content of O element is 49.53%. After finishing with 20% BiOI / ZnO / CS, the linen fabric increases N, Zn, Bi and I elements, in which the content of C element is 43.75%, the content of O element is 34.70%, the content of N element is 8.19%, the content of Zn element is 7.66%, the content of Bi element is 4.65% and the content of I element is 1.05%. From figure 2 and 3, it can be seen that the four elements of N, Zn, Bi and I introduced into the linen fabric are uniformly distributed on the linen fabric without a large amount of agglomeration, which indicates that the finishing agent 20% BiOI / ZnO / CS is uniformly combined with the linen fabric. Figure 3 4 From table 1, it can be seen that the four elements of N, Zn, Bi and I introduced into the linen fabric are uniformly distributed on the linen fabric without a large amount of agglomeration, which indicates that the finishing agent 20% BiOI / ZnO / CS is uniformly combined with the linen fabric.

[0096] Table 1 element distribution mass percentage of linen fabric before and after finishing

[0097] Element Unfinished mass percentage / % Finished mass percentage / % C 50.47 43.75 O 49.53 34.70 N 0 8.19 Zn 0 7.66 Bi 0 4.65 I 0 1.05

[0098] Bacteriostatic experiment

[0099] Figure 5 ​​​​​To arrange the antibacterial diagram of the linen fabric before and after finishing, Table 2 shows the antibacterial effect of Staphylococcus aureus and Escherichia coli of the application examples 1-5 and the comparative examples 1-4. It can be seen that the BiOI / ZnO / CS composite material prepared by the application has good antibacterial effect, and the antibacterial rate is greater than 95%. As can be seen from Table 2, with the increase of the proportion of BiOI in the composite material, the antibacterial performance is continuously increased. When the addition amount reaches 20%, the antibacterial rate reaches 100%, and when the addition amount is 25%, the antibacterial rate decreases, which indicates that the addition amount of BiOI is too large, which destroys the system of the composite material, so that it cannot exert the maximum antibacterial effect.

[0100] Table 2: Antibacterial effect of the application on Staphylococcus aureus and Escherichia coli

[0101]

[0102] Anti-ultraviolet performance:

[0103] Table 3 shows the anti-ultraviolet performance of the linen fabric after finishing of the application examples 1-5 and the comparative examples 1-4. It can be seen that the BiOI / ZnO / CS composite material prepared by the application has good anti-ultraviolet performance. As can be seen from comparative example 1, the UPF value of the linen fabric finished by CS is low, and the T(UVA) AV and T(UVB) AV values are large, which indicates that the ultraviolet protection ability is weak. As can be seen from comparative examples 2 and 3, the linen fabric finished by ZnO has good ultraviolet protection ability, and the ZnO / CS composite material is endowed with anti-ultraviolet performance. As can be seen from comparative example 4, the linen fabric finished by BiOI has good ultraviolet protection ability. As can be seen from examples 1-5, with the increase of the proportion of BiOI in the composite material, the UPF is continuously increased, and the T(UVA) AV and T(UVB) AV values are continuously reduced. When the addition amount reaches 20%, the UPF reaches 105.66, and when the addition amount is 25%, the UPF decreases, which indicates that the addition amount of BiOI is too large, which destroys the system of the composite material, so that it cannot exert the maximum anti-ultraviolet effect.

[0104] Table 3: Anti-ultraviolet performance of the application

[0105] Number UPF T(UVA)AV T(UVB)AV Example 1 68.84 2.69 1.89 Example 2 77.21 1.94 1.62 Example 3 81.02 1.83 1.77 Example 4 105.66 1.37 0.56 Example 5 96.92 1.51 0.71 Comparative Example 1 20.04 7.94 4.27 Comparative Example 2 93.04 1.95 0.98 Comparative Example 3 68.64 2.57 1.19 Comparative Example 4 91.80 1.23 1.06

[0106] Hydrophobic performance

[0107] Table 4 shows the hydrophobic properties of the flax fabrics treated in Examples 1-5 and Comparative Examples 1-4 of the present invention. It can be seen that the BiOI / ZnO / CS composite material prepared in the present invention has excellent hydrophobic properties. As can be seen from Examples 1-5 and Comparative Examples 1-3, the water contact angle of the flax fabrics treated with CS, ZnO, and ZnO / CS is less than 90°, while the water contact angle of the flax fabrics treated with BiOI and BiOI / ZnO / CS is greater than 90°. In Examples 1-5, as the proportion of BiOI in the composite material increases, the water contact angle of the treated flax fabric increases, indicating that BiOI plays a major hydrophobic role in the composite material.

[0108] Table 4 Hydrophobic properties of the present invention

[0109]

[0110]

[0111] Physical property analysis of linen fabrics

[0112] Table 5 shows the physical properties of the linen fabrics after finishing in Examples 1-5 of the present invention. It can be seen that the different proportions of BiOI / ZnO / CS composite materials prepared in the present invention do not significantly change the wrinkle recovery angle and breaking strength of the linen fabrics, indicating that the composite material does not cause damage to the linen fabrics themselves when loaded onto the fabric.

[0113] Table 5 Physical properties of the present invention

[0114] Number Crease recovery angle / ° Breaking strength / N Example 1 80.70 605 Example 2 81.20 556 Example 3 78.50 524 Example 4 79.70 599 Example 5 75.70 538 Whole front flax fabric 82.50 599

[0115] The multifunctional composite material prepared by this invention exhibits excellent antibacterial, UV-resistant, and hydrophobic effects. Considering all factors, the 20% BiOI / ZnO / CS ratio shows even better results. When applied to flax fabrics, this invention improves the antibacterial, UV-resistant, and hydrophobic properties of the flax fabrics without affecting their texture, thus achieving the performance requirements of antibacterial, UV-resistant, and hydrophobic textiles.

[0116] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0117] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and that variations, modifications, substitutions and changes can be made by those skilled in the art without departing from the scope of the present application.

Claims

1. A method for preparing a BiOI / ZnO / chitosan composite material, characterized in that, Includes the following steps: S1: Dissolve chitosan in acetic acid solution, add zinc acetate dihydrate, and stir at room temperature until dissolved; S2: In a reaction vessel with a water bath temperature of 60-70℃, add the solution from step S1, add NaOH solution dropwise until pH=9-10, stir for 3-4 h, cool to room temperature after the reaction is completed, wash several times with deionized water and ethanol until neutral, centrifuge; dry at 70-80℃ overnight, grind into powder to obtain ZnO / chitosan composite material. S3: Disperse the ZnO / chitosan composite material in ethylene glycol, sonicate for 30-60 min, and then add it to a mixed solution of Bi(NO3)3·5H2O and polyvinylpyrrolidone dissolved in ethylene glycol to obtain solution 1. The mass ratio of ZnO / chitosan composite material to Bi(NO3)3·5H2O is (3.2-4):

1. Completely dissolve KI in ethylene glycol to obtain solution 2. Slowly add solution 2 to solution 1 with vigorous stirring using a syringe, and continue stirring for 2-3 h. Transfer the mixture to a stainless steel autoclave lined with Teflon and react at 140-160 ℃ for 12-14 h. Cool to room temperature, centrifuge, wash with deionized water and ethanol, and dry overnight at 70-80 ℃ to obtain the BiOI / ZnO / chitosan composite material.

2. The method for preparing a BiOI / ZnO / chitosan composite material according to claim 1, characterized in that, The chitosan has a degree of deacetylation ≥95%, a viscosity of 100-200 mPa·s, and a molecular weight of 120,000-260,000.

3. The method for preparing a BiOI / ZnO / chitosan composite material according to claim 1, characterized in that, In step S3, the molar ratio of KI to Bi(NO3)3·5H2O is 1:1; And / or, in step S3, the mass ratio of Bi(NO3)3·5H2O to polyvinylpyrrolidone is (4.5-4.6):

1.

4. The method for preparing a BiOI / ZnO / chitosan composite material according to any one of claims 1-3, characterized in that, The concentration of the acetic acid solution is 1%; And / or, the molar ratio of chitosan to zinc acetate dihydrate is 1:1; And / or, the concentration of the NaOH solution is 1 mol / L.

5. A BiOI / ZnO / chitosan composite material, characterized in that, The BiOI / ZnO / chitosan composite material is prepared by the preparation method according to any one of claims 1-4.

6. The application of the BiOI / ZnO / chitosan composite material according to claim 5 in antibacterial and UV-resistant finishing of textiles.

7. The application according to claim 6, characterized in that, The textile is a linen fabric. The BiOI / ZnO / chitosan composite material is ultrasonically mixed with distilled water and used as a fabric finishing solution with a bath ratio of 30:1.

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