A natural plant-based antibacterial fabric and a preparation method thereof

Abstract

The application discloses a kind of natural plant-based antibacterial fabric and preparation method thereof, it is related to fiber fabric field.The application is when preparing natural plant-based antibacterial fabric, first hollow silica is loaded with zinc ion, then sequentially with epoxy butyl trimethoxysilane, aniline and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-mercapto)-guanidine are reacted, and functional hollow silica is prepared;After 30nm cotton fiber aldehyde is based, first with 3-aminopropyl methyl dimethoxysilane, dimethyl dimethoxysilane and methyl dimethoxysilane, then with allyl phosphonic acid, and functional cotton fiber is prepared;Functional cotton fiber is spun, woven, and hollow silica mixed solution is sprayed on the surface, and natural plant-based antibacterial fabric is prepared.The natural plant-based antibacterial fabric prepared by the application has the ability of antistatic, durable, flame-retardant.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of fiber fabrics, in particular to a natural plant-based antibacterial fabric and a preparation method thereof. BACKGROUND

[0002] Cotton cloth is a woven fabric made of cotton yarn. Different varieties are derived from different specifications and different post-processing methods. Cotton cloth is soft, comfortable, warm, moisture-absorbing, breathable, and easy to dye and finish. Due to its natural properties, it is loved by people and has become an indispensable basic necessity in life, commonly used in clothing, bedding, indoor supplies, interior decoration, industry, medicine, military, etc.

[0003] Cotton textiles are generally formed by spinning and weaving cotton fibers. The structure of the finished cotton fabric is in a porous state, so the surface of the cotton fabric is easy to adsorb microorganisms. Microorganisms are ubiquitous, and we may come into contact with them at any time and anywhere. The surface of the cotton fabric contains a large number of hydroxyl groups, making it have excellent water absorption. Sweat, dander, and stains accidentally adhered to the surface of the cotton fabric can provide nutrients for microorganisms. These conditions make microorganisms particularly easy to reproduce and grow on the surface of the cotton fabric, causing the performance of the cotton fabric, such as color and mechanical strength, to deteriorate, and even possibly leading to infection of the human body by bacteria. Therefore, the present application introduces a natural plant-based antibacterial fabric and a preparation method thereof. SUMMARY

[0004] A natural plant-based antibacterial fabric, which is prepared by spinning, weaving, and then spraying a functionalized hollow silica mixture solution on the surface of functionalized cotton fibers.

[0005] The functionalized cotton fibers are prepared by first aldehyde-functionalizing 30 nm cotton fibers, then reacting them with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, and methyl dimethoxysilane, and then reacting them with allyl phosphonic acid.

[0006] The functionalized hollow silica mixture solution is prepared by uniformly mixing functionalized hollow silica, N,N-dimethylformamide, and polytetrafluoroethylene.

[0007] The functionalized hollow silica is prepared by first loading zinc ions on hollow silica, and then sequentially reacting them with epoxy butyl trimethoxysilane, aniline, and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, and N-(2-mercapto)-guanidine.

[0008] A preparation method of a natural plant-based antibacterial fabric, which mainly includes the following preparation steps:

[0009] (1) uniformly mix N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol according to a mass ratio of 2-3:0.1-0.3:15-25 to prepare an N-(2-mercapto)-guanidine mixture; mix the functionalized hollow silica precursor and ethanol according to a mass ratio of 9-11:15-25, stir at 200-300 r / min for 3-5 min, warm up to 65-75℃, add the N-(2-mercapto)-guanidine mixture at a rate of 2-2.5 times the mass of the functionalized hollow silica precursor within 8-12 min, continue to stir for 2.5-3.5 h, filter, wash 3-5 times with ethanol, and vacuum dry at 55-65℃ for 11-13 h to prepare the functionalized hollow silica;

[0010] (2) uniformly mix chloroplatinic acid and deionized water according to a mass ratio of 1:90-110 to prepare a catalyst; mix the modified cotton fiber, allyl phosphonic acid, deionized water and the catalyst according to a mass ratio of 9-11:1:20-30:0.3-0.5, stir at 60-70℃ and 200-300 r / min for 4-6 h, filter, wash 3-5 times with deionized water, and vacuum dry at -10-0℃ for 22-26 h to prepare the functionalized cotton fiber;

[0011] (3) uniformly mix the functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene according to a mass ratio of 7-8:50:1-2 to prepare a functionalized hollow silica mixture; spin the functionalized cotton fiber, weave, set the spraying distance to 80 cm, spray the functionalized hollow silica mixture for 1 s each time, stand for 11-13 h at room temperature after spraying, and then spray again, with the spraying times being 6-8.

[0012] 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 according to a mass ratio of 9-11:2-3:4-4.6:30-40, stirring at 62-64℃ and 200-300 r / min for 5-7 h, filtering, washing 3-5 times with methanol, and vacuum drying at -10-0℃ for 22-26 h.

[0013] As an optimization, the modified hollow silica is prepared by mixing pre-modified hollow silica, ethanol, aniline and o-aminoacetophenone according to 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 at a rate of equal mass of the pre-modified hollow silica within 2.5-3.5 h, continuing to stir for 18-22 h, filtering, washing 5-7 times with ethanol, and vacuum drying at -10-0℃ for 22-26 h.

[0014] As optimization, the initiator solution is prepared by mixing ammonium persulfate and deionized water in a mass ratio of 1:9-11 uniformly.

[0015] As optimization, the pre-modified hollow silica is prepared by mixing zinc ion loaded hollow silica, epoxy butyl trimethoxysilane and isopropyl alcohol in a mass ratio of 1:0.14-0.16:10-12, adjusting pH to 3.8-4.2 with 0.1 mol / L acetic acid solution, stirring at 85-95℃ and 200-300 r / min for 5-7 h, filtering, washing with deionized water for 3-5 times, and drying at 90-100℃ for 2-4 h.

[0016] As optimization, the zinc ion loaded hollow silica is prepared by mixing zinc acetate and deionized water in a mass ratio of 1:3-5 to prepare zinc acetate aqueous solution, mixing 50 nm hollow silica and the zinc acetate aqueous solution in a mass ratio of 1:3-5, ultrasonicating for 25-35 min, vacuumizing to a vacuum degree of -0.1 MPa, standing for 25-35 min, restoring normal pressure, repeating vacuumizing and restoring normal pressure for 3 times, centrifuging at 4500-5500 r / min for 4-6 min, taking the solid phase, washing with ethanol for 3-5 times, and vacuum drying at -10-0℃ for 22-26 h.

[0017] As optimization, the modified cotton fiber in step (2) is prepared by mixing pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyl dimethoxysilane and deionized water in a mass ratio of 9-11:1:3-5:1:30-40, adjusting pH to 5 with 0.1 mol / L hydrochloric acid aqueous solution, stirring at room temperature and 200-300 r / min for 25-35 min, heating to 75-85℃, continuing to stir for 110-130 min, filtering, washing with deionized water for 3-5 times, and vacuum drying at -10-0℃ for 22-26 h.

[0018] As optimization, the pre-modified cotton fiber is prepared by preparing acetic acid buffer solution by preparing acetic acid, sodium acetate and deionized water into a solution with pH of 5, mixing 30 nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and the acetic acid buffer solution in a mass ratio of 9-11:0.09-0.11:0.07-0.09:90-110, stirring at 25-35℃ and 200-300 r / min for 35-37 h, filtering, washing with methanol for 3-5 times, and vacuum drying at -10-0℃ for 22-26 h.

[0019] As optimization, the spinning in step (3) refers to spinning yarns by using FA320A high-speed drawing frame, THC2015 type full-automatic doffer roving frame, TH598 type spinning frame and GMR001 type small-sized winding frame in sequence, and the drawing process is: 6 roots of blending is adopted, and the draft ratio is 1.5 times; the roving process is: the draft ratio in the rear area is 1.22 times, the roving twist factor is 120, and the roving weight is 6g / (10m); the spinning process is: the draft ratio in the rear area is 1.16 times, the gauge block specification is 3.0mm, and the spindle speed is 11000rpm.

[0020] Compared with the prior art, the application has the beneficial effects that:

[0021] In the preparation of the natural plant-based antibacterial fabric, hollow silica is first loaded with zinc ions, and then sequentially reacts with epoxy butyl trimethoxysilane, aniline and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-mercapto)-guanidine to prepare functionalized hollow silica; 30nm cotton fibers are first aldehyde-functionalized, and then sequentially react with 3-aminopropyl methyl dimethoxysilane, dimethyl dimethoxysilane and methyl dimethoxysilane, and then react with allyl phosphonic acid to prepare functionalized cotton fibers; the functionalized cotton fibers are spun, woven, and then sprayed with a hollow silica mixture on the surface to prepare a natural plant-based antibacterial fabric.

[0022] First, hollow silica is first loaded with zinc ions, and then sequentially reacts with epoxy butyl trimethoxysilane, aniline and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-mercapto)-guanidine to prepare functionalized hollow silica; the zinc ions are loaded inside the hollow silica, have redox properties, can react with organic matter (thio group, carboxyl group, hydroxyl group), can bind to bacterial cell membranes and membrane proteins, destroy their structure, destroy the enzymes of the electron transport system after entering the cells and react with DNA, thereby achieving antibacterial effect and improving the antibacterial ability of the material; then reacts with epoxy butyl trimethoxysilane, aniline and o-aminoacetophenone to polymerize polyaniline on the surface of the silica, polyaniline has high conductivity, improves the antistatic effect of the material; then reacts with 3,5-di-tert-butyl-4-hydroxybenzaldehyde to introduce a hindered phenol structure, which can react with peroxy radicals to generate hydroperoxide and phenoxy radicals, phenoxy radicals further react with other peroxy radicals to generate relatively stable products, which no longer take hydrogen atoms from the polymer main chain, thereby interrupting the radical chain reaction and preventing the continuation of the oxidation reaction, achieving the effect of aging resistance; finally, reacts with N-(2-mercapto)-guanidine, which can bind to bacterial cell membranes to destroy the normal metabolic activity of bacteria, achieving antibacterial effect and improving the antibacterial ability of the material.

[0023] Secondly, the 30nm cotton fiber is aldehyde-based, then reacts with 3-aminopropyl methyl dimethoxysilane, dimethyl dimethoxysilane and methyl dimethoxysilane, and then reacts with allyl phosphonic acid to prepare functionalized cotton fiber; the functionalized cotton fiber is spun, woven, and then sprayed with a hollow silica mixed solution on the surface to prepare a natural plant-based antibacterial fabric; the 30nm cotton fiber is aldehyde-based, then reacts with 3-aminopropyl methyl dimethoxysilane, dimethyl dimethoxysilane and methyl dimethoxysilane to form polysiloxane on the surface of the cotton fiber, the polysiloxane will decompose at high temperature to form a dense carbon layer containing aromatic groups and siloxane chains, and the carbon layer can effectively isolate heat and oxygen to prevent further thermal decomposition of the polymer material, thereby achieving the purpose of flame retardation; then reacts with allyl phosphonic acid, and the organic phosphorus can be decomposed into phosphoric acid by heat, and further dehydrated into metaphosphoric acid and poly-metaphosphoric 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, can isolate oxygen and reduce heat transfer to the substrate, inhibit the release of flammable gas, improve the flame retardant ability of the material, and because the phosphoric acid group is a protonic acid, it can stimulate the antistatic performance of polyaniline, and better combination effect with functionalized hollow silica can be achieved. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0025] The spinning in the following examples and comparative examples refers to the yarn prepared by using FA320A high-speed drawing frame, THC2015 type full-automatic doffer roving frame, TH598 type spinning frame and GMR001 type small-sized bobbin winder in sequence, and the drawing process adopts 6 ends of blending with a draft ratio of 1.5 times; the roving process adopts a back zone draft ratio of 1.22 times, a roving twist factor of 120 and a roving weight of 6g / (10m); and the spinning process adopts a back zone draft ratio of 1.16 times, a gauge block specification of 3.0mm and a spindle speed of 11000rpm. Example 1:

[0026] A preparation method of a natural plant-based antibacterial fabric mainly includes the following preparation steps:

[0027] (1) zinc acetate and deionized water were mixed according to a mass ratio of 1:3 to prepare a zinc acetate aqueous solution, 50 nm hollow silica and the zinc acetate aqueous solution were mixed according to a mass ratio of 1:3, ultrasonic treatment was performed for 25 min, vacuum was drawn to a vacuum degree of -0.1 MPa, and the system was left to stand for 25 min; the vacuum was restored to normal pressure, and the vacuum and normal pressure were alternately restored for 3 times; centrifugation was performed at 4500 r / min for 4 min, the solid phase was washed with ethanol for 3 times, and vacuum drying was performed at -10℃ for 22 h to prepare zinc ion-loaded hollow silica; the zinc ion-loaded hollow silica, epoxy butyl trimethoxysilane and isopropyl alcohol were mixed according to a mass ratio of 1:0.14:10, 0.1 mol / L acetic acid solution was used to adjust the pH to 3.8, and stirring was performed at 85℃ and 200 r / min for 5 h; filtration was performed, deionized water was used for washing 3 times, and drying was performed at 90℃ for 2 h to prepare pre-modified hollow silica; ammonium persulfate and deionized water were uniformly mixed according to a mass ratio of 1:9 to prepare an initiator solution; the pre-modified hollow silica, ethanol, aniline and o-aminoacetophenone were mixed according to a mass ratio of 9:40:3:1, stirring was performed at 100 r / min under nitrogen protection for 60 min, the initiator solution with the same mass as the pre-modified hollow silica was added at a uniform speed within 2.5 h, and stirring was continuously performed for 18 h; filtration was performed, ethanol was used for washing 5 times, and vacuum drying was performed at -10℃ for 22 h to prepare modified hollow silica; the modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide and methanol were mixed according to a mass ratio of 9:2:4:30, stirring was performed at 62℃ and 200 r / min for 5 h, filtration was performed, methanol was used for washing 3 times, and vacuum drying was performed at -10℃ for 22 h to prepare functionalized hollow silica precursor; N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol were uniformly mixed according to a mass ratio of 2:0.1:15 to prepare an N-(2-mercapto)-guanidine mixture; the functionalized hollow silica precursor and ethanol were mixed according to a mass ratio of 9:15, stirring was performed at 200 r / min for 3 min, the temperature was raised to 65℃, the N-(2-mercapto)-guanidine mixture with a mass of 2 times that of the functionalized hollow silica precursor was added at a uniform speed within 8 min, stirring was continuously performed for 2.5 h, filtration was performed, ethanol was used for washing 3 times, and vacuum drying was performed at 55℃ for 11 h to prepare functionalized hollow silica;

[0028] (2) acetic acid, sodium acetate and deionized water were prepared into a solution with pH 5 to prepare an acetic acid buffer solution; 30 nm cotton fibers, laccase, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and the acetic acid buffer solution were mixed at a mass ratio of 9:0.09:0.07:90, stirred at 25 DEG C and 200 r / min for 35 h, filtered, washed with methanol for 3 times, and vacuum dried at -10 DEG C for 22 h to prepare a pre-modified cotton fiber; the pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyl dimethoxysilane and deionized water were mixed at a mass ratio of 9:1:3:1:30, the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid aqueous solution, stirred at room temperature and 200 r / min for 25 min, heated to 75 DEG C, and continued to stir for 110 min, filtered, washed with deionized water for 3 times, and vacuum dried at -10 DEG C for 22 h to prepare a modified cotton fiber; chloroplatinic acid and deionized water were uniformly mixed at a mass ratio of 1:90 to prepare a catalyst; the modified cotton fiber, allyl phosphonic acid, deionized water and the catalyst were mixed at a mass ratio of 9:1:20:0.3, stirred at 60 DEG C and 200 r / min for 4 h, filtered, washed with deionized water for 3 times, and vacuum dried at -10 DEG C for 22 h to prepare a functionalized cotton fiber;

[0029] (3) the functionalized hollow silica was uniformly mixed with N,N-dimethylformamide and polytetrafluoroethylene at a mass ratio of 7:50:1 to prepare a functionalized hollow silica mixture; the functionalized cotton fiber was spun, woven, and set to a spraying distance of 80 cm and a spraying time of 1 s each time, and the functionalized hollow silica mixture was sprayed, and after spraying, it was placed at room temperature for 11 h, and then the next spraying was performed, and the spraying was performed 6 times. Example 2:

[0030] A preparation method of a natural plant-based antibacterial fabric mainly includes the following preparation steps:

[0031] (1) zinc acetate and deionized water were mixed according to a mass ratio of 1:4 to prepare a zinc acetate aqueous solution, 50 nm hollow silica and the zinc acetate aqueous solution were mixed according to a mass ratio of 1:4, and ultrasonic treatment was performed for 30 min; vacuum was applied to a vacuum degree of -0.1 MPa, and the system was left to stand for 30 min; normal pressure was restored, and the vacuum and normal pressure restoration were repeated for 3 times; centrifugation was performed at 5000 r / min for 5 min, and the solid phase was washed with ethanol for 4 times and vacuum dried at -5℃ for 24 h to prepare zinc ion-loaded hollow silica; the zinc ion-loaded hollow silica, epoxy butyl trimethoxysilane and isopropyl alcohol were mixed according to a mass ratio of 1:0.15:11, 0.1 mol / L acetic acid solution was used to adjust the pH to 4, and stirring was performed at 90℃ and 250 r / min for 6 h; filtration was performed, and the product was washed with deionized water for 4 times and dried at 95℃ for 3 h to prepare pre-modified hollow silica; ammonium persulfate and deionized water were uniformly mixed according to a mass ratio of 1:10 to prepare an initiator solution; the pre-modified hollow silica, ethanol, aniline and o-aminoacetophenone were mixed according to a mass ratio of 10:45:4:1, and stirring was performed under nitrogen protection at 150 r / min for 70 min; the initiator solution in an amount equal to that of the pre-modified hollow silica was added at a uniform speed within 3 h, and stirring was continuously performed for 20 h; filtration was performed, and the product was washed with ethanol for 5 times and vacuum dried at -5℃ for 24 h to prepare modified hollow silica; the modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide and methanol were mixed according to a mass ratio of 10:2.5:4.3:35, and stirring was performed at 63℃ and 250 r / min for 6 h; filtration was performed, and the product was washed with methanol for 4 times and vacuum dried at -5℃ for 24 h to prepare functionalized hollow silica precursor; N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol were uniformly mixed according to a mass ratio of 2.5:0.2:20 to prepare an N-(2-mercapto)-guanidine mixture; the functionalized hollow silica precursor and ethanol were mixed according to a mass ratio of 10:20, and stirring was performed at 250 r / min for 4 min; the functionalized hollow silica precursor was heated to 70℃, and the N-(2-mercapto)-guanidine mixture in an amount of 2.25 times that of the functionalized hollow silica precursor was added at a uniform speed within 10 min; stirring was continuously performed for 3 h; filtration was performed, and the product was washed with ethanol for 4 times and vacuum dried at 60℃ for 12 h to prepare functionalized hollow silica.

[0032] (2) acetic acid, sodium acetate and deionized water were prepared into a solution with pH 5 to prepare an acetic acid buffer solution; 30 nm cotton fibers, laccase, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and the acetic acid buffer solution were mixed at a mass ratio of 10:0.1:0.08:100, stirred at 30°C and 250 r / min for 36 h, filtered, washed with methanol 4 times, and vacuum dried at-5°C for 24 h to prepare a pre-modified cotton fiber; the pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyl dimethoxysilane and deionized water were mixed at a mass ratio of 10:1:4:1:35, the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid aqueous solution, stirred at room temperature and 250 r / min for 30 min, heated to 80°C and continued to stir for 120 min, filtered, washed with deionized water 4 times, and vacuum dried at-5°C for 24 h to prepare a modified cotton fiber; chloroplatinic acid and deionized water were uniformly mixed at a mass ratio of 1:100 to prepare a catalyst; the modified cotton fiber, allyl phosphonic acid, deionized water and the catalyst were mixed at a mass ratio of 10:1:25:0.4, stirred at 65°C and 250 r / min for 5 h, filtered, washed with deionized water 4 times, and vacuum dried at-5°C for 24 h to prepare a functionalized cotton fiber;

[0033] (3) the functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene were uniformly mixed at a mass ratio of 7.5:50:1.5 to prepare a functionalized hollow silica mixture; the functionalized cotton fiber was spun, woven, and set to a spraying distance of 80 cm and a spraying time of 1 s each time, and the functionalized hollow silica mixture was sprayed, and after spraying, it was placed at room temperature for 12 h, and then the next spraying was performed, and the spraying number was 7 times. Example 3:

[0034] A preparation method of a natural plant-based antibacterial fabric mainly includes the following preparation steps:

[0035] (1) zinc acetate and deionized water were mixed according to a mass ratio of 1:5 to prepare a zinc acetate aqueous solution, 50 nm hollow silica and the zinc acetate aqueous solution were mixed according to a mass ratio of 1:5, ultrasonic treatment was performed for 35 min, vacuum was drawn to a vacuum degree of -0.1 MPa, and the system was left to stand for 35 min; the vacuum was restored to normal pressure, and the vacuum and normal pressure were alternately restored for 3 times; centrifugation was performed at 5500 r / min for 6 min, the solid phase was washed with ethanol for 5 times, and vacuum drying was performed at 0℃ for 26 h to prepare zinc ion-loaded hollow silica; the zinc ion-loaded hollow silica, epoxy butyl trimethoxysilane and isopropyl alcohol were mixed according to a mass ratio of 1:0.16:12, a pH value was adjusted to 4.2 with a 0.1 mol / L acetic acid solution, and stirring was performed at 95℃ and 300 r / min for 7 h; filtration was performed, deionized water was used for washing 5 times, and drying was performed at 100℃ for 4 h to prepare pre-modified hollow silica; ammonium persulfate and deionized water were uniformly mixed according to a mass ratio of 1:11 to prepare an initiator solution; the pre-modified hollow silica, ethanol, aniline and o-aminoacetophenone were mixed according to a mass ratio of 11:50:5:1, stirring was performed at 200 r / min under nitrogen protection for 80 min, the initiator solution with the same mass as the pre-modified hollow silica was added at a uniform speed within 3.5 h, and stirring was continuously performed for 22 h; filtration was performed, ethanol was used for washing 7 times, and vacuum drying was performed at 0℃ for 26 h to prepare modified hollow silica; the modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide and methanol were mixed according to a mass ratio of 11:3:4.6:40, stirring was performed at 64℃ and 300 r / min for 7 h, filtration was performed, methanol was used for washing 5 times, and vacuum drying was performed at 0℃ for 26 h to prepare functionalized hollow silica precursor; N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol were uniformly mixed according to a mass ratio of 3:0.3:25 to prepare an N-(2-mercapto)-guanidine mixture; the functionalized hollow silica precursor and ethanol were mixed according to a mass ratio of 11:25, stirring was performed at 300 r / min for 5 min, the temperature was raised to 75℃, the N-(2-mercapto)-guanidine mixture with a mass of 2.5 times that of the functionalized hollow silica precursor was added at a uniform speed within 12 min, stirring was continuously performed for 3.5 h, filtration was performed, ethanol was used for washing 5 times, and vacuum drying was performed at 65℃ for 13 h to prepare functionalized hollow silica;

[0036] (2) acetic acid, sodium acetate and deionized water were prepared into a solution with pH 5 to prepare an acetic acid buffer solution; 30 nm cotton fibers, laccase, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and the acetic acid 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 with methanol for 5 times, and vacuum dried at 0℃ for 26 h to prepare a pre-modified cotton fiber; the pre-modified cotton fiber, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyl dimethoxysilane and deionized water were mixed at a mass ratio of 11:1:5:1:40, the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid aqueous solution, stirred at room temperature and 300 r / min for 35 min, heated to 85℃, and continued to stir for 130 min, filtered, washed with deionized water for 5 times, and vacuum dried at 0℃ for 26 h to prepare a modified cotton fiber; chloroplatinic acid and deionized water were uniformly mixed at a mass ratio of 1:110 to prepare a catalyst; the modified cotton fiber, allyl phosphonic acid, deionized water and the catalyst were mixed at a mass ratio of 11:1:30:0.5, stirred at 70℃ and 300 r / min for 6 h, filtered, washed with deionized water for 5 times, and vacuum dried at 0℃ for 26 h to prepare a functionalized cotton fiber;

[0037] (3) the functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene were uniformly mixed at a mass ratio of 8:50:2 to prepare a functionalized hollow silica mixture; the functionalized cotton fiber was spun, woven, and set to a spraying distance of 80 cm, a spraying time of 1 s each time, and the functionalized hollow silica mixture was sprayed, and after spraying, it was placed at room temperature for 13 h, and then the next spraying was carried out, and the spraying number was 8 times.

[0038] Comparative Example 1

[0039] The preparation method of the natural plant-based antibacterial fabric of Comparative Example 1 is different from that of Example 2 in that step (1) is modified as follows: zinc acetate and deionized water are mixed at a mass ratio of 1:4 to prepare a zinc acetate aqueous solution, 50 nm hollow silica is mixed with the zinc acetate aqueous solution at a mass ratio of 1:4, ultrasonic treatment is performed for 30 min, vacuum is drawn to a vacuum degree of -0.1 MPa, and the system is left to stand for 30 min; the vacuum is restored to normal pressure, and the vacuum restoration to normal pressure is repeated 3 times; centrifugation is performed at 5000 r / min for 5 min, the solid phase is washed with ethanol 4 times, and vacuum drying is performed at -5℃ for 24 h to prepare zinc ion-loaded hollow silica; the zinc ion-loaded hollow silica, epoxy butyl trimethoxysilane, and isopropyl alcohol are mixed at a mass ratio of 1:0.15:11, the pH is adjusted to 4 with a 0.1 mol / L acetic acid solution, stirring is performed at 90℃ and 250 r / min for 6 h, filtration is performed, washing with deionized water is performed 4 times, and drying is performed at 95℃ for 3 h to prepare pre-modified hollow silica; ammonium persulfate and deionized water are uniformly mixed at a mass ratio of 1:10 to prepare an initiator solution; the pre-modified hollow silica, ethanol, aniline, and o-aminoacetophenone are mixed at a mass ratio of 10:45:4:1, stirring is performed at 150 r / min under nitrogen protection for 70 min, the initiator solution of the same mass as the pre-modified hollow silica is added at a uniform speed within 3 h, stirring is continued for 20 h, filtration is performed, washing with ethanol is performed 5 times, and vacuum drying is performed at -5℃ for 24 h to prepare modified hollow silica; the modified hollow silica, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, potassium hydroxide, and methanol are mixed at a mass ratio of 10:2.5:4.3:35, stirring is performed at 63℃ and 250 r / min for 6 h, filtration is performed, washing with methanol is performed 4 times, and vacuum drying is performed at -5℃ for 24 h to prepare functionalized hollow silica. The remaining steps are the same as those of Example 2.

[0040] Comparative Example 2:

[0041] The preparation method of the natural plant-based antibacterial fabric of Comparative Example 2 is different from that of Example 2 in that step (1) is modified. In step (1), zinc acetate and deionized water are mixed at a mass ratio of 1:4 to prepare a zinc acetate aqueous solution, 50 nm hollow silica is mixed with the zinc acetate aqueous solution at a mass ratio of 1:4, ultrasonic treatment is performed for 30 min, vacuum is drawn to a vacuum degree of -0.1 MPa, standing is performed for 30 min, normal pressure is restored, vacuum drawing and normal pressure restoration are repeated for 3 times, centrifugation is performed at 5000 r / min for 5 min, the solid phase is washed with ethanol for 4 times, vacuum drying is performed at -5℃ for 24 h, and functionalized hollow silica is prepared. The remaining steps are the same as those of Example 2.

[0042] Comparative Example 3:

[0043] The preparation method of the natural plant-based antibacterial fabric of Comparative Example 3 is different from that of Example 2 in that step (1) is modified. In step (1), zinc acetate and deionized water are mixed at a mass ratio of 1:4 to prepare a zinc acetate aqueous solution, 50 nm hollow silica is mixed with the zinc acetate aqueous solution at a mass ratio of 1:4, ultrasonic treatment is performed for 30 min, vacuum is drawn to a vacuum degree of -0.1 MPa, standing is performed for 30 min, normal pressure is restored, vacuum drawing and normal pressure restoration are repeated for 3 times, centrifugation is performed at 5000 r / min for 5 min, the solid phase is washed with ethanol for 4 times, vacuum drying is performed at -5℃ for 24 h, and functionalized hollow silica is prepared. The remaining steps are the same as those of Example 2.

[0044] Comparative Example 4:

[0045] The preparation method of the natural plant-based antibacterial fabric of Comparative Example 4 is different from that of Example 2 in that the hollow silica is not modified. The remaining steps are the same as those of Example 2.

[0046] Comparative Example 5:

[0047] The preparation method of the natural plant-based antibacterial fabric of Comparative Example 5 is different from that of Example 2 in that 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 acetic acid buffer; 30 nm cotton fibers, laccase, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and the acetic acid buffer are mixed at a mass ratio of 10:0.1:0.08:100, stirred at 30°C and 250 r / min for 36 h, filtered, washed with methanol 4 times, and vacuum dried at -5°C for 24 h to obtain pre-modified cotton fibers; the pre-modified cotton fibers, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, methyl dimethoxysilane and deionized water are mixed at a mass ratio of 10:1:4:1:35, the pH is adjusted to 5 with 0.1 mol / L hydrochloric acid aqueous solution, stirred at room temperature and 250 r / min for 30 min, heated to 80°C and continuously stirred for 120 min, filtered, washed with deionized water 4 times, and vacuum dried at -5°C for 24 h to obtain functionalized cotton fibers;

[0048] Comparative Example 6:

[0049] The preparation method of the natural plant-based antibacterial fabric of Comparative Example 6 is different from that of Example 2 in that the 30 nm cotton fibers are not modified. The remaining steps are the same as those of Example 2.

[0050] Test Example 1:

[0051] Antibacterial test:

[0052] Test method: tested according to GB / T20944, wherein the selected bacteria are Staphylococcus aureus and Escherichia coli. The results are shown in Table 1.

[0053] Table 1

[0054]

[0055] It can be found from the experimental data in Table 1 that the natural plant-based antibacterial fabric prepared by the application has good antibacterial ability.

[0056] It can be found from the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 1 that the bacteriostatic rates of Examples 1, 2 and 3 are high. The difference between Comparative Example 1 and the examples is that guanidine is not introduced on the surface of hollow silica through the reaction of thiol and alkene in Comparative Example 1. Guanidine can bind to bacterial cell membranes and destroy the normal metabolic activity of bacteria, achieving antibacterial effect and improving the antibacterial ability of the material.

[0057] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4, it can be found that the bacteriostatic rates of Examples 1, 2 and 3 are high, and the difference between Comparative Example 4 and the examples is that no guanidine is introduced on the surface of the hollow silica by the reaction of thiol and alkene, and no zinc ion is loaded in the hollow silica, and the zinc ion has redox property, can react with organic matters (thio group, carboxyl group, hydroxyl group), can combine with bacterial cell membrane and membrane protein, destroy the structure, destroy the enzyme of electron transfer system after entering the cell and react with DNA, so as to achieve the antibacterial effect and improve the antibacterial ability of the material.

[0058] Test Example 2:

[0059] Flame retardant and antistatic test:

[0060] Flame retardant test: test the limiting oxygen index according to the test standard GB / T5454-1997;

[0061] Waterproof test: use a contact angle measuring instrument to test the water contact angle of the fabric woven by the fibers prepared in each example and comparative example;

[0062] Antistatic test: according to FZ / T01042-1996 "Determination of Static Performance and Static Voltage of Textile Materials", cut the fabric prepared in each example and comparative example into 60mm*80mm, and measure the half-life period of the sample on YG(L)342D fabric voltage tester under the condition of relative humidity of 35% and temperature of 20℃. The results are shown in Table 2.

[0063] Table 2

[0064]

[0065] From the comparison of the experimental data in Table 2, it can be found that the natural plant-based antibacterial fabric prepared by the application has good flame retardant and antistatic ability.

[0066] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3 in Table 2, it can be found that the half-life periods of Examples 1, 2 and 3 are short, and the difference between Comparative Example 3 and the examples is that no polyaniline is formed on the surface of the hollow silica, and the polyaniline has high conductivity, which can improve the antistatic ability of the material;

[0067] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 5, it can be found that the half-life periods of Examples 1, 2 and 3 are short, and the difference between Comparative Example 5 and the examples is that no phosphoric acid group is introduced on the surface of the cotton fiber, and there is no protonic acid to cause protonation reaction of the nitrogen atom on the imine;

[0068] From the experimental data comparison of examples 1, 2, 3 and comparative example 5, it can be found that the limiting oxygen index of examples 1, 2, 3 is high, and the difference between comparative example 5 and examples is that no phosphoric acid group is introduced on the surface of the cotton fiber, and the organic phosphorus can be decomposed into phosphoric acid by heat, and further dehydrated into metaphosphoric acid and poly-metaphosphoric acid, which catalyzes the dehydration and carbonization of the polymer surface to form a dense carbon layer, the carbon layer has low thermal conductivity and non-flammability, can isolate oxygen and reduce heat transfer to the substrate, inhibit the release of flammable gas, and improve the flame retardant ability of the material;

[0069] From the experimental data comparison of examples 1, 2, 3 and comparative example 6, it can be found that the limiting oxygen index of examples 1, 2, 3 is high, and the difference between comparative example 6 and examples is that no polysiloxane is formed on the surface of the cotton fiber, and the polysiloxane will decompose at high temperature to form a dense carbon layer containing aromatic groups and siloxane chains, which can effectively isolate heat and oxygen and prevent further thermal decomposition of the polymer material, thereby achieving the purpose of flame retardation.

[0070] Test example 3:

[0071] Aging resistance test:

[0072] Test method: the single yarn of the fabric prepared in each example and comparative example is tested, the single yarn tensile strength of each example and comparative example is tested by using YG061F electronic single yarn strength tester according to GB / T14344 standard, and is recorded as M0; after irradiation for 15 days by using fluorescent ultraviolet lamp UV-A340 according to ISO4892-3 international standard, the single yarn tensile strength is tested again, and is recorded as M1, and the retention rate is calculated, wherein the retention rate = M1 / M0 x 100%. The results are shown in table 3.

[0073] Table 3

[0074]

[0075] From the experimental data comparison in table 3, it can be found that the natural plant-based antibacterial fabric prepared by the application has good durability.

[0076] From the experimental data comparison of examples 1, 2, 3 and comparative example 2 in table 3, it can be found that the retention rate of examples 1, 2, 2 is high, and the difference between comparative example 2 and examples is that no hindered phenol is introduced on the surface of the hollow silica, and the hindered phenol can react with the peroxy free radical to generate hydroperoxide and phenoxy free radical, and the phenoxy free radical further reacts with other peroxy free radicals to generate relatively stable products, which no longer take hydrogen atoms from the polymer main chain, thereby interrupting the free radical chain reaction and preventing the continuous progress of the oxidation reaction, and achieving the aging resistance effect.

[0077] The above detailed description of the specific embodiments of the present application has been given to understand the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A natural plant-based antibacterial fabric, characterized in that, The natural plant-based antibacterial fabric is prepared by spinning the functionalized cotton fiber, weaving, and then spraying a functionalized hollow silica mixed solution on the surface. The functionalized cotton fiber is prepared by first aldehyde-based 30nm cotton fiber, then reacting with 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane and methyl dimethoxysilane, and then reacting with allyl phosphonic acid. The functionalized hollow silica mixed solution is prepared by uniformly mixing functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene. The functionalized hollow silica is prepared by first loading zinc ions on hollow silica, and then sequentially reacting with epoxy butyl trimethoxysilane, aniline and o-aminoacetophenone, 3,5-di-tert-butyl-4-hydroxybenzaldehyde and N-(2-mercapto)-guanidine.

2. A method of preparing a natural plant-based antibacterial fabric, characterized by, The preparation method of the natural plant-based antibacterial fabric mainly includes the following preparation steps: (1) uniformly mix N-(2-mercapto)-guanidine, azobisisobutyronitrile and ethanol according to a mass ratio of 2-3:0.1-0.3:15-25 to prepare an N-(2-mercapto)-guanidine mixed solution; mix the functionalized hollow silica precursor and ethanol according to a mass ratio of 9-11:15-25, stir at 200-300 r / min for 3-5 min, heat to 65-75℃, uniformly add the N-(2-mercapto)-guanidine mixed solution with a mass of 2-2.5 times of the functionalized hollow silica precursor within 8-12 min, continue to stir for 2.5-3.5 h, filter, wash with ethanol for 3-5 times, and vacuum dry at 55-65℃ for 11-13 h to prepare the functionalized hollow silica; (2) uniformly mix chloroplatinic acid and deionized water according to a mass ratio of 1:90-110 to prepare a catalyst; mix modified cotton fiber, allyl phosphonic acid, deionized water and the catalyst according to a mass ratio of 9-11:1:20-30:0.3-0.5, stir at 60-70℃ and 200-300 r / min for 4-6 h, filter, wash with deionized water for 3-5 times, and vacuum dry at -10-0℃ for 22-26 h to prepare the functionalized cotton fiber; (3) uniformly mix the functionalized hollow silica, N,N-dimethylformamide and polytetrafluoroethylene according to a mass ratio of 7-8:50:1-2 to prepare a functionalized hollow silica mixed solution; spin the functionalized cotton fiber, weave, set the spraying distance to 80 cm, spray the functionalized hollow silica mixed solution for 1 s each time, stand still at room temperature for 11-13 h after spraying, and then spray again, the spraying times are 6-8 times.

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

4. A method of 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 initiator solution of the same mass as the pre-modified hollow silica at a uniform speed within 2.5-3.5 h, continuing to stir for 18-22 h, filtering, washing with ethanol for 5-7 times, and vacuum drying at-10-0 ℃ for 22-26 h.

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

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

7. A method of preparing a natural plant-based antibacterial fabric according to claim 6, characterized in that, The zinc ion loaded hollow silica is prepared by mixing zinc acetate and deionized water in a mass ratio of 1:3-5 to prepare zinc acetate aqueous solution, mixing 50 nm hollow silica and the zinc acetate aqueous solution in a mass ratio of 1:3-5, ultrasonicating for 25-35 min, vacuumizing to a vacuum degree of-0.1 MPa, standing for 25-35 min, restoring normal pressure, repeating vacuumizing and restoring normal pressure for 3 times, centrifuging at 4500-5500 r / min for 4-6 min, taking the solid phase, washing with ethanol for 3-5 times, and vacuum drying at-10-0 ℃ for 22-26 h.

8. A method of 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, methyl dimethoxysilane and deionized water in a mass ratio of 9-11:1:3-5:1:30-40, adjusting the pH to 5 with 0.1 mol / L hydrochloric acid aqueous solution, stirring at room temperature and 200-300 r / min for 25-35 min, heating to 75-85 ℃, continuing to stir for 110-130 min, filtering, washing with deionized water for 3-5 times, and vacuum drying at-10-0 ℃ for 22-26 h.

9. A method of preparing a natural plant-based antibacterial fabric according to claim 8, characterized in that, The pre-modified cotton fiber is prepared by preparing acetic acid buffer solution by preparing a solution of acetic acid, sodium acetate and deionized water to a pH of 5, mixing 30 nm cotton fiber, laccase, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical and the acetic acid buffer solution in a mass ratio of 9-11:0.09-0.11:0.07-0.09:90-110, stirring at 25-35 ℃ and 200-300 r / min for 35-37 h, filtering, washing with methanol for 3-5 times, and vacuum drying at-10-0 ℃ for 22-26 h.

10. A method of preparing a natural plant-based antibacterial fabric according to claim 2, characterized in that, The spinning in step (3) refers to spinning yarns by using FA320A high-speed drawing frame, THC2015 type automatic doffer roving frame, TH598 type spinning frame and GMR001 type small winding frame in sequence, the drawing process is: 6 ends are adopted for doubling, the draft ratio is 1.5 times; the roving process is: the draft ratio in the back zone is 1.22 times, the roving twist factor is 120, and the roving weight is 6 g / (10 m); the spinning process is: the draft ratio in the back zone is 1.16 times, the gauge block specification is 3.0 mm, and the spindle speed is 11000 rpm.

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