Natural plant-based antibacterial fabric and preparation method thereof

Abstract

The invention discloses a natural plant-based antibacterial fabric and a preparation method thereof, and relates to the field of fiber fabrics. When the natural plant-based antibacterial fabric is prepared, hollow silicon dioxide is firstly loaded with zinc ions and then sequentially reacts with epoxy butyl trimethoxy silane, aniline, o-aminoacetophenone, 3, 5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-sulfydryl)-guanidine, and functional hollow silicon dioxide is prepared; the preparation method comprises the following steps: carrying out formylation on 30nm cotton fibers, and then reacting the 30nm cotton fibers with 3-aminopropyl methyl dimethoxy silane, dimethyl dimethoxy silane, methyl dimethoxy silane and allyl phosphonic acid to prepare functional cotton fibers; the functional cotton fibers are spun and woven, then the hollow silicon dioxide mixed solution is sprayed on the surface, and the natural plant-based antibacterial fabric is prepared. The natural plant-based antibacterial fabric prepared by the invention has antistatic, durable and flame-retardant capabilities.

Description

Technical Field

[0001] This invention relates to the field of fiber fabrics, specifically to a natural plant-based antibacterial fabric and its preparation method. Background Technology

[0002] Cotton fabric is a woven fabric made from cotton yarn. Different varieties are derived from different weave specifications and post-processing methods. Cotton fabric is characterized by its softness and comfort, warmth, moisture absorption, breathability, and ease of dyeing and finishing. Due to these natural properties, it is loved by people and has become an indispensable basic item in life. It is often used for clothing, bedding, indoor products, interior decoration, industry, medical care, military and other fields.

[0003] Cotton textiles are generally made from cotton fibers through spinning, dyeing, and weaving. The resulting cotton fabrics have a porous structure, making them highly susceptible to microbial adsorption. Microorganisms are ubiquitous, and we may come into contact with them anytime and anywhere. Furthermore, the large number of hydroxyl groups on the surface of cotton fabrics gives them excellent water absorption. Sweat, dander, and stains that accidentally adhere to the surface of cotton fabrics can provide nutrients for microorganisms. These conditions make it particularly easy for microorganisms to multiply and grow on the surface of cotton fabrics, causing a decline in the fabric's color, mechanical strength, and other properties, and may even lead to bacterial infections in humans. Therefore, this application introduces a natural plant-based antibacterial fabric and its preparation method. Summary of the Invention

[0004] A natural plant-based antibacterial fabric is made by spinning and weaving functionalized cotton fibers, and then spraying a hollow silica mixture onto the surface to obtain the natural plant-based antibacterial fabric. The functionalized cotton fiber is prepared by aldehyde-modifying 30nm cotton fiber and then reacting it with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane and methyldimethoxysilane, followed by reaction with allylphosphonic acid. The hollow silica mixture is prepared by uniformly mixing functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene. The functionalized hollow silica is prepared by first loading zinc ions onto hollow silica and then reacting it sequentially with epoxybutyltrimethoxysilane, aniline and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-mercapto)-guanidine.

[0005] A method for preparing a natural plant-based antibacterial fabric, the method mainly comprising the following preparation steps: (1) N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol are mixed evenly at a mass ratio of 2~3:0.1~0.3:15~25 to obtain N-(2-mercapto)-guanidine mixture; functionalized hollow silica precursor and ethanol are mixed at a mass ratio of 9~11:15~25, stirred at 200~300r / min for 3~5min, heated to 65~75℃, and N-(2-mercapto)-guanidine mixture with a mass ratio of 2~2.5 times that of functionalized hollow silica precursor is added uniformly within 8~12min, stirred for 2.5~3.5h, filtered, washed with ethanol 3~5 times, and vacuum dried at 55~65℃ for 11~13h to obtain functionalized hollow silica; (2) Chloroplatinic acid and deionized water are mixed evenly at a mass ratio of 1:90~110 to obtain a catalyst; modified cotton fiber, allylphosphonic acid, deionized water and catalyst are mixed at a mass ratio of 9~11:1:20~30:0.3~0.5, stirred at 60~70℃ and 200~300r / min for 4~6h, filtered, washed with deionized water 3~5 times, and vacuum dried at -10~0℃ for 22~26h to obtain functionalized cotton fiber; (3) Mix functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene in a mass ratio of 7~8:50:1~2 to obtain a functionalized hollow silica mixture; spin functionalized cotton fibers, weave them, set the spraying distance to 80cm, the spraying time to 1s each time, spray the functionalized hollow silica mixture, let it stand at room temperature for 11~13h after spraying, and then spray again. The number of spraying times is 6~8 times.

[0006] As an optimization, the functionalized hollow silica precursor in step (1) is prepared by mixing modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide and methanol in a mass ratio of 9~11:2~3:4~4.6:30~40, stirring at 62~64℃ and 200~300r / min for 5~7h, filtering, washing with methanol 3~5 times, and vacuum drying at -10~0℃ for 22~26h.

[0007] As an optimization, the modified hollow silica is prepared by mixing pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone in a mass ratio of 9~11:40~50:3~5:1, stirring at 100~200 r / min under nitrogen protection for 60~80 min, adding an initiator solution of equal mass to the pre-modified hollow silica at a uniform rate over 2.5~3.5 h, continuing stirring for 18~22 h, filtering, washing with ethanol 5~7 times, and vacuum drying at -10~0℃ for 22~26 h.

[0008] As an optimization, the initiator solution is prepared by mixing ammonium persulfate and deionized water at a mass ratio of 1:9~11.

[0009] As an optimization, the pre-modified hollow silica is prepared by mixing zinc-loaded hollow silica, epoxybutyltrimethoxysilane, and isopropanol in a mass ratio of 1:0.14~0.16:10~12, adjusting the pH to 3.8~4.2 with 0.1mol / L acetic acid solution, stirring at 85~95℃ and 200~300r / min for 5~7h, filtering, washing with deionized water 3~5 times, and drying at 90~100℃ for 2~4h.

[0010] As an optimization, the zinc-loaded hollow silica is prepared by mixing zinc acetate and deionized water at a mass ratio of 1:3~5 to obtain a zinc acetate aqueous solution. 50nm hollow silica is then mixed with the zinc acetate aqueous solution at a mass ratio of 1:3~5, ultrasonicated for 25~35 min, evacuated to a vacuum degree of -0.1MPa, allowed to stand for 25~35 min, and restored to normal pressure. The vacuum restoration to normal pressure is repeated 3 times. The mixture is then centrifuged at 4500~5500r / min for 4~6 min, and the solid phase is washed 3~5 times with ethanol and vacuum dried at -10~0℃ for 22~26 h.

[0011] As an optimization, the modified cotton fiber in step (2) is prepared by mixing pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyldimethoxysilane and deionized water in a mass ratio of 9~11:1:3~5:1:30~40, adjusting the pH to 5 with 0.1mol / L hydrochloric acid aqueous solution, stirring at 200~300r / min for 25~35min at room temperature, raising the temperature to 75~85℃, continuing to stir for 110~130min, filtering, washing with deionized water 3~5 times, and vacuum drying at -10~0℃ for 22~26h.

[0012] As an optimization, the pre-modified cotton fiber is prepared by preparing an acetate buffer solution with a pH of 5 using acetic acid, sodium acetate, and deionized water. 30nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxy radical, and acetate buffer are mixed at a mass ratio of 9~11:0.09~0.11:0.07~0.09:90~110 and stirred at 25~35℃ and 200~300r / min for 35~37h. The mixture is then filtered, washed 3~5 times with methanol, and vacuum dried at -10~0℃ for 22~26h.

[0013] As an optimization, the spinning in step (3) refers to spinning by sequentially using a FA320A high-speed drawing frame, a THC2015 fully automatic doffing roving frame, a TH598 spinning frame, and a GMR001 small winding machine. The drawing process is as follows: 6 yarns are drawn together, and the draft ratio is 1.5 times. The roving process is as follows: the back zone draft ratio is 1.22 times, the roving twist coefficient is 120, and the roving weight is 6g / (10m). The spinning process is as follows: the back zone draft ratio is 1.16 times, the spacer block specification is 3.0mm, and the spindle speed is 11000rpm.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing natural plant-based antibacterial fabrics, this invention involves first loading zinc ions onto hollow silica and then reacting it sequentially with epoxybutyltrimethoxysilane, aniline, o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, and N-(2-mercapto)-guanidine to obtain functionalized hollow silica. Then, aldehyde-modified 30nm cotton fibers are reacted with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, and methyldimethoxysilane, followed by allylphosphonic acid to obtain functionalized cotton fibers. These functionalized cotton fibers are then spun, woven, and finally coated with a hollow silica mixture to obtain the natural plant-based antibacterial fabric.

[0015] First, hollow silica is loaded with zinc ions and then reacted sequentially with epoxybutyltrimethoxysilane, aniline, o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, and N-(2-mercapto)-guanidine to prepare functionalized hollow silica. The zinc ions loaded inside the hollow silica possess redox properties and can react with organic matter (thiogroups, carboxyl groups, hydroxyl groups). They can bind to bacterial cell membranes and membrane proteins, disrupting their structure. After entering the cell, they disrupt the enzymes of the electron transport system and react with DNA, thereby achieving an antibacterial effect and improving the material's antibacterial ability. Then, it reacts with epoxybutyltrimethoxysilane, aniline, and o-aminoacetophenone to polymerize polyaniline on the silica surface. The phosphate group acts as a protonic acid; during the doping process, the hydrogen ions generated from the decomposition can move to the polyaniline molecular chain, causing the nitrogen atoms on the imine to undergo a protonation reaction, generating charged elements. The excited-state polaron protonates on the imine nitrogen atom of the molecular chain, generating a charged excited-state polaron. This creates a hole in the doped valence band of polyaniline, causing the quinone ring to disappear and the electron cloud to redistribute. The positive charge on the nitrogen atom is delocalized into the large conjugated bond, giving polyaniline high conductivity and improving the material's antistatic effect. Further reaction with 3,5-di-tert-butyl-4-hydroxybenzaldehyde introduces a hindered phenolic structure, which can react with peroxide free radicals to generate hydroperoxides and phenoxy free radicals. The phenoxy free radicals further react with other peroxide free radicals to generate relatively stable products that no longer abstract hydrogen atoms from the polymer backbone, thus interrupting the free radical chain reaction and preventing further oxidation, achieving anti-aging effects. Finally, reaction with N-(2-mercapto)-guanidine allows guanidine to bind to bacterial cell membranes, disrupting normal bacterial metabolism and achieving an antibacterial effect, thus improving the material's antibacterial capability.

[0016] Secondly, 30nm cotton fibers are aldehyde-modified and then reacted with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, and methyldimethoxysilane, followed by allylphosphonic acid, to obtain functionalized cotton fibers. These functionalized cotton fibers are then spun, woven, and coated with a hollow silica mixture to produce a natural plant-based antibacterial fabric. Alternatively, 30nm cotton fibers are aldehyde-modified and then reacted with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, and methyldimethoxysilane to form polysiloxane on the surface of the cotton fibers. This polysiloxane decomposes at high temperatures, forming a dense carbon layer containing aromatic groups and silicon oxide chains. This carbon layer can effectively insulate heat and oxygen, preventing further thermal decomposition of polymer materials, thereby achieving flame retardancy. Upon reaction with allylphosphonic acid, the organophosphorus can decompose thermally to generate phosphoric acid, which is further dehydrated into metaphosphoric acid and polymetaphosphoric acid. These acidic substances catalyze the dehydration and carbonization of the polymer surface, forming a dense carbon layer. This carbon layer has low thermal conductivity and is non-flammable, isolating oxygen and reducing heat transfer to the substrate, inhibiting the release of combustible gases, and improving the flame retardancy of the material. Furthermore, because the phosphoric acid group is a protic acid, it can stimulate the antistatic properties of polyaniline and achieve better bonding with functionalized hollow silica. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] The spinning described in the following examples and comparative examples refers to spinning using a FA320A high-speed drawing frame, a THC2015 fully automatic doffing roving frame, a TH598 spinning frame, and a GMR001 small winding machine in sequence. The drawing process is as follows: 6 yarns are drawn together, and the draft ratio is 1.5. The roving process is as follows: the back zone draft ratio is 1.22, the roving twist coefficient is 120, and the roving weight is 6g / (10m). The spinning process is as follows: the back zone draft ratio is 1.16, the spacer block size is 3.0mm, and the spindle speed is 11000rpm. Example 1:

[0019] A method for preparing a natural plant-based antibacterial fabric mainly includes the following preparation steps: (1) Zinc acetate and deionized water were mixed at a mass ratio of 1:3 to prepare an aqueous solution of zinc acetate. 50 nm hollow silica was mixed with the aqueous solution of zinc acetate at a mass ratio of 1:3. The mixture was sonicated for 25 min, evacuated to a vacuum degree of -0.1 MPa, allowed to stand for 25 min, and then returned to normal pressure. The evacuation and restoration to normal pressure were repeated 3 times. The mixture was centrifuged at 4500 r / min for 4 min, and the solid phase was washed 3 times with ethanol. The solid phase was then vacuum dried at -10℃ for 22 h to obtain zinc ion-loaded hollow silica. Zinc ion-loaded hollow silica and epoxybutyltrimethoxysilane were then mixed. Ammonium persulfate and isopropanol were mixed at a mass ratio of 1:0.14:10, and the pH was adjusted to 3.8 with 0.1 mol / L acetic acid solution. The mixture was stirred at 85℃ and 200 r / min for 5 h, filtered, washed three times with deionized water, and dried at 90℃ for 2 h to obtain pre-modified hollow silica. Ammonium persulfate and deionized water were mixed evenly at a mass ratio of 1:9 to obtain an initiator solution. Pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone were mixed at a mass ratio of 9:40:3:1 and stirred at 100 r / min under nitrogen protection for 60 min. An initiator solution of equal mass to pre-modified hollow silica was added uniformly over 2.5 hours, and stirring was continued for 18 hours. The mixture was then filtered, washed five times with ethanol, and vacuum dried at -10°C for 22 hours to obtain modified hollow silica. Modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide, and methanol were mixed at a mass ratio of 9:2:4:30, stirred at 62°C and 200 r / min for 5 hours, filtered, washed three times with methanol, and vacuum dried at -10°C for 22 hours to obtain a functionalized hollow silica precursor. N-( N-(2-mercapto)-guanidine, azobisisobutyronitrile, and ethanol were mixed uniformly at a mass ratio of 2:0.1:15 to obtain an N-(2-mercapto)-guanidine mixture. The functionalized hollow silica precursor and ethanol were mixed at a mass ratio of 9:15 and stirred at 200 r / min for 3 min. The mixture was heated to 65 °C and N-(2-mercapto)-guanidine mixture, twice the mass of the functionalized hollow silica precursor, was added uniformly over 8 min. The mixture was stirred for 2.5 h, filtered, washed three times with ethanol, and vacuum dried at 55 °C for 11 h to obtain functionalized hollow silica. (2) Acetic acid, sodium acetate and deionized water were prepared into a solution with a pH of 5 to obtain an acetate buffer solution; 30 nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxy radical and acetate buffer solution were mixed at a mass ratio of 9:0.09:0.07:90, stirred at 25℃ and 200 r / min for 35 h, filtered, washed 3 times with methanol, and vacuum dried at -10℃ for 22 h to obtain pre-modified cotton fiber; pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyldimethoxysilane and deionized water were mixed at a mass ratio of 9:1:3:1:30 and 0. The pH was adjusted to 5 with a 1 mol / L hydrochloric acid aqueous solution. The mixture was stirred at 200 r / min for 25 min at room temperature, then heated to 75 °C and stirred for another 110 min. After filtration, the mixture was washed three times with deionized water and dried under vacuum at -10 °C for 22 h to obtain modified cotton fibers. Chloroplatinic acid and deionized water were mixed evenly at a mass ratio of 1:90 to obtain a catalyst. Modified cotton fibers, allylphosphonic acid, deionized water, and the catalyst were mixed at a mass ratio of 9:1:20:0.3 and stirred at 200 r / min for 4 h at 60 °C. After filtration, the mixture was washed three times with deionized water and dried under vacuum at -10 °C for 22 h to obtain functionalized cotton fibers. (3) Functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene are mixed evenly at a mass ratio of 7:50:1 to prepare a functionalized hollow silica mixture; functionalized cotton fibers are spun and woven, the spraying distance is set to 80cm, the spraying time is 1s each time, the functionalized hollow silica mixture is sprayed, and after spraying, it is left to stand at room temperature for 11h, and then the next spraying is carried out. The number of spraying times is 6. Example 2:

[0020] A method for preparing a natural plant-based antibacterial fabric mainly includes the following preparation steps: (1) Zinc acetate and deionized water were mixed at a mass ratio of 1:4 to prepare an aqueous solution of zinc acetate. 50 nm hollow silica was mixed with the aqueous solution of zinc acetate at a mass ratio of 1:4. The mixture was sonicated for 30 min, evacuated to a vacuum degree of -0.1 MPa, allowed to stand for 30 min, and then allowed to return to normal pressure. The evacuation and return to normal pressure were repeated 3 times. The mixture was centrifuged at 5000 r / min for 5 min, and the solid phase was washed 4 times with ethanol. The solid phase was then vacuum dried at -5℃ for 24 h to obtain zinc ion-loaded hollow silica. Zinc ion-loaded hollow silica, epoxybutyltrimethoxysilane and isobutylene oxide were then mixed. Propanol was mixed at a mass ratio of 1:0.15:11, and the pH was adjusted to 4 with 0.1 mol / L acetic acid solution. The mixture was stirred at 90℃ and 250 r / min for 6 h, filtered, washed four times with deionized water, and dried at 95℃ for 3 h to obtain pre-modified hollow silica. Ammonium persulfate and deionized water were mixed evenly at a mass ratio of 1:10 to obtain an initiator solution. Pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone were mixed at a mass ratio of 10:45:4:1, stirred at 150 r / min under nitrogen protection for 70 min, and then dried at 3... An initiator solution of equal mass to that of pre-modified hollow silica was added uniformly over h, and stirring was continued for 20 h. The mixture was then filtered, washed five times with ethanol, and vacuum dried at -5℃ for 24 h to obtain modified hollow silica. Modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide, and methanol were mixed at a mass ratio of 10:2.5:4.3:35, stirred at 63℃ and 250 r / min for 6 h, filtered, washed four times with methanol, and vacuum dried at -5℃ for 24 h to obtain a functionalized hollow silica precursor. N-(2-mercapto) N-(2-mercapto)-guanidine, azobisisobutyronitrile, and ethanol were mixed uniformly at a mass ratio of 2.5:0.2:20 to obtain an N-(2-mercapto)-guanidine mixture. The functionalized hollow silica precursor and ethanol were mixed at a mass ratio of 10:20 and stirred at 250 r / min for 4 min. The mixture was heated to 70 °C, and 2.25 times the mass of the functionalized hollow silica precursor N-(2-mercapto)-guanidine mixture was added uniformly over 10 min. The mixture was stirred for 3 h, filtered, washed 4 times with ethanol, and vacuum dried at 60 °C for 12 h to obtain functionalized hollow silica. (2) Acetic acid, sodium acetate and deionized water were prepared into a solution with a pH of 5 to obtain an acetate buffer solution; 30 nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxy radical and acetate buffer solution were mixed at a mass ratio of 10:0.1:0.08:100, stirred at 30℃ and 250 r / min for 36 h, filtered, washed 4 times with methanol, and vacuum dried at -5℃ for 24 h to obtain pre-modified cotton fiber; pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyldimethoxysilane and deionized water were mixed at a mass ratio of 10:1:4:1:35 and 0. The pH was adjusted to 5 with a 1 mol / L hydrochloric acid aqueous solution. The mixture was stirred at 250 r / min for 30 min at room temperature, then heated to 80℃ and stirred for another 120 min. After filtration, the mixture was washed four times with deionized water and vacuum dried at -5℃ for 24 h to obtain modified cotton fibers. Chloroplatinic acid and deionized water were mixed evenly at a mass ratio of 1:100 to obtain a catalyst. Modified cotton fibers, allylphosphonic acid, deionized water, and the catalyst were mixed at a mass ratio of 10:1:25:0.4 and stirred at 250 r / min for 5 h at 65℃. After filtration, the mixture was washed four times with deionized water and vacuum dried at -5℃ for 24 h to obtain functionalized cotton fibers. (3) Functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene are mixed evenly in a mass ratio of 7.5:50:1.5 to prepare a functionalized hollow silica mixture; functionalized cotton fibers are spun and woven, the spraying distance is set to 80cm, the spraying time is 1s each time, the functionalized hollow silica mixture is sprayed, and after spraying, it is left to stand at room temperature for 12h before the next spraying is carried out. The number of spraying times is 7. Example 3:

[0021] A method for preparing a natural plant-based antibacterial fabric mainly includes the following preparation steps: (1) Zinc acetate and deionized water were mixed at a mass ratio of 1:5 to prepare an aqueous solution of zinc acetate. 50 nm hollow silica was mixed with the aqueous solution of zinc acetate at a mass ratio of 1:5. The mixture was sonicated for 35 min, evacuated to a vacuum degree of -0.1 MPa, allowed to stand for 35 min, and then restored to normal pressure. The evacuation and restoration to normal pressure were repeated 3 times. The mixture was centrifuged at 5500 r / min for 6 min. The solid phase was washed 5 times with ethanol and dried under vacuum at 0℃ for 26 h to obtain zinc ion-loaded hollow silica. Zinc ion-loaded hollow silica, epoxybutyltrimethoxysilane and isopropyl... Alcohols were mixed at a mass ratio of 1:0.16:12, and the pH was adjusted to 4.2 with 0.1 mol / L acetic acid solution. The mixture was stirred at 95℃ and 300 r / min for 7 h, filtered, washed 5 times with deionized water, and dried at 100℃ for 4 h to obtain pre-modified hollow silica. Ammonium persulfate and deionized water were mixed evenly at a mass ratio of 1:11 to obtain an initiator solution. Pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone were mixed at a mass ratio of 11:50:5:1 and stirred at 200 r / min under nitrogen protection for 80 min. An initiator solution of equal mass to pre-modified hollow silica was added uniformly over 3.5 hours, and stirring was continued for 22 hours. The mixture was then filtered, washed seven times with ethanol, and vacuum dried at 0°C for 26 hours to obtain modified hollow silica. Modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide, and methanol were mixed at a mass ratio of 11:3:4.6:40, stirred at 64°C and 300 r / min for 7 hours, filtered, washed five times with methanol, and vacuum dried at 0°C for 26 hours to obtain a functionalized hollow silica precursor. N-(2-mercapto-2-hydroxybenzaldehyde) N-(2-mercapto)-guanidine, azobisisobutyronitrile, and ethanol were mixed uniformly at a mass ratio of 3:0.3:25 to obtain an N-(2-mercapto)-guanidine mixture. The functionalized hollow silica precursor and ethanol were mixed at a mass ratio of 11:25 and stirred at 300 r / min for 5 min. The mixture was heated to 75 °C, and N-(2-mercapto)-guanidine mixture with a mass of 2.5 times that of the functionalized hollow silica precursor was added uniformly over 12 min. The mixture was stirred for 3.5 h, filtered, washed 5 times with ethanol, and vacuum dried at 65 °C for 13 h to obtain functionalized hollow silica. (2) Acetic acid, sodium acetate, and deionized water were prepared into a solution with a pH of 5 to obtain an acetate buffer solution; 30 nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxy radical, and acetate buffer solution were mixed at a mass ratio of 11:0.11:0.09:110, stirred at 35℃ and 300 r / min for 37 h, filtered, washed 5 times with methanol, and vacuum dried at 0℃ for 26 h to obtain pre-modified cotton fiber; pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyldimethoxysilane, and deionized water were mixed at a mass ratio of 11:1:5:1:40, and dried at 0℃ for 26 h to obtain pre-modified cotton fiber. The pH was adjusted to 5 with a 0.1 mol / L hydrochloric acid aqueous solution. The mixture was stirred at 300 r / min for 35 min at room temperature, then heated to 85 °C and stirred for another 130 min. After filtration, the mixture was washed five times with deionized water and dried under vacuum at 0 °C for 26 h to obtain modified cotton fiber. Chloroplatinic acid and deionized water were mixed evenly at a mass ratio of 1:110 to obtain a catalyst. Modified cotton fiber, allylphosphonic acid, deionized water and catalyst were mixed at a mass ratio of 11:1:30:0.5 and stirred at 300 r / min for 6 h at 70 °C. After filtration, the mixture was washed five times with deionized water and dried under vacuum at 0 °C for 26 h to obtain functionalized cotton fiber. (3) Functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene are mixed evenly in a mass ratio of 8:50:2 to prepare a functionalized hollow silica mixture; functionalized cotton fibers are spun and woven, the spraying distance is set to 80cm, the spraying time is 1s each time, the functionalized hollow silica mixture is sprayed, and after spraying, it is left to stand at room temperature for 13h, and then the next spraying is carried out. The number of spraying times is 8.

[0022] Comparative Example 1: The difference between the preparation method of the natural plant-based antibacterial fabric in Comparative Example 1 and Example 2 lies in the different steps (1). Step (1) is modified as follows: Zinc acetate and deionized water are mixed at a mass ratio of 1:4 to obtain a zinc acetate aqueous solution. 50nm hollow silica is mixed with the zinc acetate aqueous solution at a mass ratio of 1:4, ultrasonicated for 30 min, vacuumed to a vacuum degree of -0.1MPa, allowed to stand for 30 min, restored to normal pressure, and the vacuum restoration was repeated 3 times. The mixture was centrifuged at 5000r / min for 5 min, and the solid phase was washed 4 times with ethanol and vacuum dried at -5℃ for 24 h to obtain zinc ion-loaded hollow silica. Zinc ion-loaded hollow silica, epoxybutyltrimethoxysilane and isopropanol are mixed at a mass ratio of 1:0.15:11, the pH is adjusted to 4 with 0.1mol / L acetic acid solution, stirred at 90℃ and 250r / min for 6 h, filtered, and washed with deionized water. The pre-modified hollow silica was washed four times and dried at 95℃ for 3 hours to obtain pre-modified hollow silica. Ammonium persulfate and deionized water were mixed evenly at a mass ratio of 1:10 to prepare an initiator solution. Pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone were mixed at a mass ratio of 10:45:4:1 and stirred at 150 r / min under nitrogen protection for 70 min. An equal mass of the initiator solution was added to the pre-modified hollow silica at a uniform rate over 3 hours, and the stirring continued. The mixture was stirred for 20 hours, filtered, washed five times with ethanol, and vacuum dried at -5°C for 24 hours to obtain modified hollow silica. The modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide, and methanol were mixed at a mass ratio of 10:2.5:4.3:35, stirred at 63°C and 250 r / min for 6 hours, filtered, washed four times with methanol, and vacuum dried at -5°C for 24 hours to obtain functionalized hollow silica. The remaining steps were the same as in Example 2.

[0023] Comparative Example 2: The difference between the preparation method of the natural plant-based antibacterial fabric in Comparative Example 2 and Example 2 lies in the different step (1). Step (1) is modified as follows: Zinc acetate and deionized water are mixed at a mass ratio of 1:4 to obtain a zinc acetate aqueous solution. 50nm hollow silica is mixed with the zinc acetate aqueous solution at a mass ratio of 1:4, ultrasonicated for 30 min, vacuumed to a vacuum degree of -0.1MPa, allowed to stand for 30 min, restored to normal pressure, and the vacuum restoration was repeated 3 times. The mixture was centrifuged at 5000r / min for 5 min, the solid phase was washed 4 times with ethanol, and vacuum dried at -5℃ for 24 h to obtain zinc ion-loaded hollow silica. Zinc ion-loaded hollow silica, epoxybutyltrimethoxysilane and isopropanol are mixed at a mass ratio of 1:0.15. The following mixtures were prepared: 1:1, ethanol, aniline, and o-aminoacetophenone were mixed, pH adjusted to 4 with 0.1 mol / L acetic acid solution, stirred at 90℃ and 250 r / min for 6 h, filtered, washed 4 times with deionized water, and dried at 95℃ for 3 h to obtain pre-modified hollow silica; ammonium persulfate and deionized water were mixed evenly at a mass ratio of 1:10 to obtain an initiator solution; pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone were mixed at a mass ratio of 10:45:4:1, stirred at 150 r / min under nitrogen protection for 70 min, and an equal mass of the initiator solution was added uniformly over 3 h, stirring continued for 20 h, filtered, washed 5 times with ethanol, and dried under vacuum at -5℃ for 24 h to obtain functionalized hollow silica. The remaining steps were the same as in Example 2.

[0024] Comparative Example 3: The difference between the preparation method of the natural plant-based antibacterial fabric in Comparative Example 3 and Example 2 lies in the different step (1). Step (1) is modified as follows: Zinc acetate and deionized water are mixed at a mass ratio of 1:4 to obtain a zinc acetate aqueous solution. 50nm hollow silica is mixed with the zinc acetate aqueous solution at a mass ratio of 1:4, sonicated for 30 min, vacuumed to a vacuum degree of -0.1MPa, left to stand for 30 min, restored to normal pressure, and the vacuum restoration was repeated 3 times. The mixture was centrifuged at 5000r / min for 5 min, the solid phase was washed 4 times with ethanol, and vacuum dried at -5℃ for 24 h to obtain functionalized hollow silica. The remaining steps are the same as in Example 2.

[0025] Comparative Example 4: The preparation method of the natural plant-based antibacterial fabric in Comparative Example 4 differs from that in Example 2 in that the hollow silica is not modified. The remaining steps are the same as in Example 2.

[0026] Comparative Example 5: The difference between the preparation method of the natural plant-based antibacterial fabric in Comparative Example 5 and Example 2 lies in step (2). Step (2) is modified as follows: Acetic acid, sodium acetate and deionized water are prepared into a solution with a pH of 5 to obtain an acetate buffer solution; 30nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxy radical and acetate buffer solution are mixed at a mass ratio of 10:0.1:0.08:100, stirred at 30℃ and 250r / min for 36h, filtered, washed 4 times with methanol, and then at -5℃. Pre-modified cotton fiber was obtained by vacuum drying for 24 h. The pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyldimethoxysilane and deionized water were mixed in a mass ratio of 10:1:4:1:35. The pH was adjusted to 5 with 0.1 mol / L hydrochloric acid aqueous solution. The mixture was stirred at 250 r / min for 30 min at room temperature, heated to 80℃ and stirred for another 120 min. The mixture was filtered, washed 4 times with deionized water, and vacuum dried at -5℃ for 24 h to obtain functionalized cotton fiber. Comparative Example 6: The preparation method of the natural plant-based antibacterial fabric in Comparative Example 6 differs from that in Example 2 in that the 30nm cotton fibers are not modified. The remaining steps are the same as in Example 2.

[0027] Test Example 1: Antibacterial test: Test method: The test was conducted according to GB / T20944, with Staphylococcus aureus and Escherichia coli selected as the bacterial species. The results are shown in Table 1.

[0028] Table 1

[0029] A comparison of the experimental data in Table 1 shows that the natural plant-based antibacterial fabric prepared by this invention has good antibacterial ability.

[0030] A comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 1 shows that Examples 1, 2, and 3 have high antibacterial rates. The difference between Comparative Example 1 and Examples is that guanidine was not introduced into the hollow silica surface through the reaction of thiol and alkene. Guanidine can bind to the bacterial cell membrane, disrupt the normal metabolic activities of bacteria, achieve antibacterial effect, and improve the antibacterial ability of the material. A comparison of the experimental data from Examples 1, 2, 3 and Comparative Example 4 reveals that Examples 1, 2, and 3 exhibit high antibacterial rates. The difference between Comparative Example 4 and the Examples lies in the absence of guanidine introduced onto the surface of hollow silica through the reaction of thiol groups with olefins, and the absence of zinc ions loaded inside the hollow silica. Zinc ions possess redox properties and can react with organic matter (thiols, carboxyl groups, hydroxyl groups). They can bind to bacterial cell membranes and membrane proteins, disrupting their structure. After entering the cell, they destroy enzymes in the electron transport system and react with DNA, thereby achieving an antibacterial effect and improving the antibacterial ability of the material.

[0031] Test Example 2: Flame retardant and antistatic tests: Flame retardancy test: The limiting oxygen index is tested according to the GB / T5454—1997 test standard; Waterproof test: The water contact angle of the fabrics woven from the fibers obtained in each embodiment and comparative example was tested using a contact angle measuring instrument. Antistatic test: Referring to FZ / T01042--1996 "Determination of electrostatic properties and static voltage of textile materials", the fabrics prepared in each example and comparative example were cut into 60mm×80mm pieces. The half-life of the samples was measured on a YG(L)342D fabric voltage tester under the conditions of 35% relative humidity and 20℃. The results are shown in Table 2.

[0032] Table 2

[0033] A comparison of the experimental data in Table 2 shows that the natural plant-based antibacterial fabric prepared by this invention has good flame retardant and antistatic properties.

[0034] A comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3 in Table 2 reveals that Examples 1, 2, and 3 have shorter half-lives. The difference between Comparative Example 3 and the Examples is that polyaniline was not formed on the surface of hollow silica. The functionalized cotton fiber surface contains phosphate groups, which act as protonic acids. During the doping process, the hydrogen ions generated by the decomposition can move to the molecular chain of polyaniline, causing the nitrogen atom on the imine to undergo a protonation reaction, generating charged excited-state polarons. This causes holes to appear in the doped valence band of polyaniline, resulting in the disappearance of the quinone ring within the molecule, the redistribution of the electron cloud, and the delocalization of the positive charge on the nitrogen atom into the large conjugated bond, making polyaniline exhibit high conductivity and improving the antistatic ability of the material. Comparison of experimental data from Examples 1, 2, 3 and Comparative Example 5 reveals that Examples 1, 2, and 3 have short half-lives. The difference between Comparative Example 5 and the Examples is that no phosphate groups were introduced on the surface of the cotton fibers, resulting in the absence of protonic acid and the inability to protonate the nitrogen atoms on the imine. A comparison of the experimental data from Examples 1, 2, 3 and Comparative Example 5 reveals that Examples 1, 2, and 3 have high limiting oxygen indices. The difference between Comparative Example 5 and the Examples is that no phosphate groups were introduced onto the surface of the cotton fibers. Organic phosphoric acid can be thermally decomposed to generate phosphoric acid, which is further dehydrated into metaphosphoric acid and polymetaphosphoric acid. These acidic substances catalyze the dehydration and carbonization of the polymer surface to form a dense carbon layer. The carbon layer has low thermal conductivity and is non-flammable, which can isolate oxygen and reduce heat transfer to the substrate, inhibit the release of combustible gases, and improve the flame retardancy of the material. A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Example 6 reveals that Examples 1, 2, and 3 exhibit high limiting oxygen indices. The difference between Comparative Example 6 and the Examples lies in the absence of polysiloxane formation on the cotton fiber surface. Polysiloxane decomposes at high temperatures, forming a dense char layer containing aromatic groups and silicon oxide chains. This char layer effectively insulates against heat and oxygen, preventing further thermal decomposition of the polymer material, thereby achieving flame retardancy. Test Example 3: Aging resistance test: Test method: Single yarns from the fabrics prepared in each example and comparative example were tested. First, the tensile strength of the single yarns in each example and comparative example was tested using a YG061F electronic single yarn tensile tester according to GB / T14344 standard, and recorded as M0. Then, according to ISO4892-3 international standard, the tensile strength of the single yarns was tested again after 15 days of irradiation with a fluorescent ultraviolet lamp UV-A340, and recorded as M1. The retention rate was calculated, where retention rate = M1 / M0 × 100%. The results are shown in Table 3.

[0035] Table 3

[0036] A comparison of the experimental data in Table 3 shows that the natural plant-based antibacterial fabric prepared by this invention has good durability.

[0037] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Example 2 in Table 3 reveals that Examples 1, 2, and 2 exhibit higher retention rates. The difference between Comparative Example 2 and the Examples lies in the absence of hindered phenolic compounds introduced onto the surface of the hollow silica. Hindered phenolic compounds can react with peroxide free radicals to generate hydroperoxides and phenoxy free radicals. These phenoxy free radicals further react with other peroxide free radicals to generate relatively stable products that no longer abstract hydrogen atoms from the polymer backbone, thus interrupting the free radical chain reaction and preventing the continued oxidation reaction, thereby achieving an anti-aging effect. The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A natural plant-based antibacterial fabric, characterized in that, The natural plant-based antibacterial fabric is made by spinning and weaving functionalized cotton fibers, and then spraying a hollow silica mixture onto the surface to obtain the natural plant-based antibacterial fabric. The functionalized cotton fiber is prepared by aldehyde-modifying 30nm cotton fiber and then reacting it with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane and methyldimethoxysilane, followed by reaction with allylphosphonic acid. The hollow silica mixture is prepared by uniformly mixing functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene. The functionalized hollow silica is prepared by first loading zinc ions onto hollow silica and then reacting it sequentially with epoxybutyltrimethoxysilane, aniline and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-mercapto)-guanidine.

2. A method for preparing a natural plant-based antibacterial fabric, characterized in that, The preparation method of the natural plant-based antibacterial fabric mainly includes the following preparation steps: (1) N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol are mixed evenly at a mass ratio of 2~3:0.1~0.3:15~25 to obtain N-(2-mercapto)-guanidine mixture; functionalized hollow silica precursor and ethanol are mixed at a mass ratio of 9~11:15~25, stirred at 200~300r / min for 3~5min, heated to 65~75℃, and N-(2-mercapto)-guanidine mixture with a mass ratio of 2~2.5 times that of functionalized hollow silica precursor is added uniformly within 8~12min, stirred for 2.5~3.5h, filtered, washed with ethanol 3~5 times, and vacuum dried at 55~65℃ for 11~13h to obtain functionalized hollow silica; (2) Chloroplatinic acid and deionized water are mixed evenly at a mass ratio of 1:90~110 to obtain a catalyst; modified cotton fiber, allylphosphonic acid, deionized water and catalyst are mixed at a mass ratio of 9~11:1:20~30:0.3~0.5, stirred at 60~70℃ and 200~300r / min for 4~6h, filtered, washed with deionized water 3~5 times, and vacuum dried at -10~0℃ for 22~26h to obtain functionalized cotton fiber; (3) Mix functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene in a mass ratio of 7~8:50:1~2 to obtain a functionalized hollow silica mixture; spin functionalized cotton fibers, weave them, set the spraying distance to 80cm, the spraying time to 1s each time, spray the functionalized hollow silica mixture, let it stand at room temperature for 11~13h after spraying, and then spray again. The number of spraying times is 6~8 times.

3. The method for preparing a natural plant-based antibacterial fabric according to claim 2, characterized in that, The functionalized hollow silica precursor in step (1) is prepared by mixing modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide and methanol in a mass ratio of 9~11:2~3:4~4.6:30~40, stirring at 62~64℃ and 200~300r / min for 5~7h, filtering, washing with methanol 3~5 times, and vacuum drying at -10~0℃ for 22~26h.

4. The method for preparing a natural plant-based antibacterial fabric according to claim 3, characterized in that, The modified hollow silica is prepared by mixing pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone in a mass ratio of 9~11:40~50:3~5:1, stirring at 100~200 r / min under nitrogen protection for 60~80 min, adding an initiator solution of equal mass to the pre-modified hollow silica at a uniform rate over 2.5~3.5 h, continuing stirring for 18~22 h, filtering, washing with ethanol 5~7 times, and vacuum drying at -10~0℃ for 22~26 h.

5. The method for preparing a natural plant-based antibacterial fabric according to claim 4, characterized in that, The initiator solution is prepared by mixing ammonium persulfate and deionized water at a mass ratio of 1:9~11.

6. The method for preparing a natural plant-based antibacterial fabric according to claim 4, characterized in that, The pre-modified hollow silica is prepared by mixing zinc-loaded hollow silica, epoxybutyltrimethoxysilane, and isopropanol in a mass ratio of 1:0.14~0.16:10~12, adjusting the pH to 3.8~4.2 with 0.1mol / L acetic acid solution, stirring at 85~95℃ and 200~300r / min for 5~7h, filtering, washing 3~5 times with deionized water, and drying at 90~100℃ for 2~4h.

7. The method for preparing a natural plant-based antibacterial fabric according to claim 6, characterized in that, The zinc-loaded hollow silica is prepared by mixing zinc acetate and deionized water at a mass ratio of 1:3-5 to obtain an aqueous solution of zinc acetate. 50nm hollow silica is then mixed with the aqueous solution of zinc acetate at a mass ratio of 1:3-5, ultrasonicated for 25-35 minutes, evacuated to a vacuum degree of -0.1MPa, allowed to stand for 25-35 minutes, and allowed to return to normal pressure. This process of evacuating to normal pressure is repeated 3 times. The mixture is then centrifuged at 4500-5500 r / min for 4-6 minutes. The solid phase is washed 3-5 times with ethanol and then vacuum dried at -10-0℃ for 22-26 hours.

8. The method for preparing a natural plant-based antibacterial fabric according to claim 2, characterized in that, The modified cotton fiber in step (2) is prepared by mixing pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyldimethoxysilane and deionized water in a mass ratio of 9~11:1:3~5:1:30~40, adjusting the pH to 5 with 0.1mol / L hydrochloric acid aqueous solution, stirring at 200~300r / min for 25~35min at room temperature, raising the temperature to 75~85℃, continuing to stir for 110~130min, filtering, washing with deionized water 3~5 times, and vacuum drying at -10~0℃ for 22~26h.

9. The method for preparing a natural plant-based antibacterial fabric according to claim 8, characterized in that, The pre-modified cotton fiber is prepared by preparing an acetate buffer solution with a pH of 5 using acetic acid, sodium acetate, and deionized water. 30nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxy radical, and acetate buffer are mixed at a mass ratio of 9~11:0.09~0.11:0.07~0.09:90~110 and stirred at 25~35℃ and 200~300 r / min for 35~37 h. The mixture is then filtered, washed 3~5 times with methanol, and vacuum dried at -10~0℃ for 22~26 h.

10. The method for preparing a natural plant-based antibacterial fabric according to claim 2, characterized in that, The spinning process in step (3) refers to spinning using a FA320A high-speed drawing frame, a THC2015 fully automatic doffing roving frame, a TH598 spinning frame, and a GMR001 small winding machine in sequence. The drawing process uses 6 yarns combined and the draft ratio is 1.

5. The roving process has a back zone draft ratio of 1.22, a roving twist coefficient of 120, and a roving weight of 6g / (10m). The spinning process has a back zone draft ratio of 1.16, a spacer block specification of 3.0mm, and a spindle speed of 11000rpm.

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