Antibacterial thermal insulation fiber material for clothing and preparation method thereof

Abstract

The present invention discloses a method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the following steps: (1) preparing an antibacterial matrix powder; (2) preparing a cyclodextrin dopamine polymer; (3) preparing a γ-aminopropyltriethoxysilane surface-modified powder; and (4) adding the antibacterial matrix powder, the cyclodextrin dopamine polymer, and the surface-modified powder to a viscose spinning solution, stirring the mixture for more than 2 hours to uniformly mix the mixture after adding the materials, standing the mixture under a negative pressure environment to remove bubbles, then wet spinning the mixture, coagulating and forming the mixture, washing the mixture with deionized water after forming, and drying the mixture to obtain the fiber material. The fiber material prepared by the method of the present invention has good antibacterial properties and a certain strength, meets the standard requirement of a bacteriostasis rate of ≥70%, and improves the pollution resistance and durability of the fiber material for clothing.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial fiber fabrics, and in particular to an antibacterial thermal insulation fiber material for clothing and a preparation method thereof. Background Art

[0002] Polyester fibers are widely used in clothing fabrics due to their excellent properties, including high breaking strength, excellent elasticity, heat resistance, abrasion resistance, and light resistance. However, during daily wear, polyester fabrics are contaminated by human sweat, sebum secretions, and dandruff. These contaminants provide a breeding ground for microbial growth, leading to mold growth and odor, significantly affecting wearer comfort. As consumers become increasingly concerned about their personal health, the requirements for the antimicrobial efficacy and durability of polyester fibers are becoming increasingly stringent. Therefore, the development of polyester fibers with antimicrobial properties is becoming increasingly important. Summary of the Invention

[0003] To this end, the present invention provides a method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the following steps:

[0004] (1) Deionized water is poured into a reactor, and then citric acid, glycine, and urea are added to the deionized water and stirred to dissolve under an ultrasonic environment; the reactor is sealed and heated to 150-170°C for hydrothermal insulation; after the insulation is completed, it is naturally cooled to room temperature, and the product is dialyzed in a dialysis membrane to remove unreacted citric acid, glycine, and urea. The dialyzed solution is concentrated under reduced pressure and freeze-dried to obtain an antibacterial matrix powder;

[0005] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, then adding dopamine hydrochloride to the solution under stirring, heating to 35±5°C in a water bath after the addition is completed, stirring for more than 5 hours, then separating the solid and liquid, and drying the solid phase to obtain a cyclodextrin dopamine polymer;

[0006] (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, heating in a water bath to 50±5° C. after the addition is completed, stirring at constant temperature for more than 1 hour, then separating the solid and liquid, and drying the solid phase to obtain a surface-modified powder;

[0007] (4) adding the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution, stirring for more than 2 hours to mix the materials evenly, standing under a negative pressure environment to remove bubbles, and then wet spinning and coagulation forming. After forming, washing with deionized water and drying to obtain the fiber material.

[0008] Furthermore, in step (1), the citric acid, glycine, and urea are added to deionized water in a ratio of citric acid: glycine: urea: deionized water = 16-18 g: 2-4 g: 8-12 g: 100 mL; and the hydrothermal insulation time at 150-170° C. is 3-4 h.

[0009] Furthermore, in the step (2), the concentration of the cyclodextrin in the cyclodextrin solution is 0.7-1.0 g / 100 mL; the amount ratio of the added amount of the dopamine hydrochloride to the cyclodextrin solution is dopamine hydrochloride:cyclodextrin solution = 0.1-0.2 g:100 mL.

[0010] Furthermore, in step (2), the concentration of the Tris buffer used is 50 mM, and the pH is 8.5.

[0011] Furthermore, in step (3), in the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 3% to 5%, and the solvent is ethanol; the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50 to 100.

[0012] Furthermore, in step (4), the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution in a mass ratio of antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 1-2:1-5:3-6:100.

[0013] The beneficial effects of the present invention are: the fiber material prepared by the method of the present invention has good antibacterial properties and a certain strength, meets the standard requirement of ≥70% antibacterial rate, and improves the pollution resistance and durability of the fiber material for clothing. By comparing Example 3 and each comparative example, it can be seen that adding the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder prepared by the present invention to the traditional fiber material is the key to achieving the antibacterial properties and improving the strength of the fiber material. This may be due to: loading the amino acid type carbon quantum dot antibacterial matrix powder of the present invention on the surface of the fiber material, on the one hand, utilizing the characteristics of the carbon quantum dot surface functional groups that can interact with the microbial cell membrane, destroying the integrity of the bacterial cell membrane, thereby improving the bactericidal effect, while adding glycine can significantly increase the number of amino groups, thereby improving the adhesion strength of the antibacterial matrix powder to the fiber material. On the other hand, the amino acid type carbon quantum dot antibacterial matrix powder can form a carbon layer on the fiber surface, which acts as a barrier to heat and gas and improves the warmth retention of the fiber material. Secondly, surface-modified copper peroxide powder is added to improve the binding force between copper peroxide powder and cyclodextrin dopamine polymer and fiber material. The copper peroxide particles gradually decompose and release hydroxyl radicals (·OH) and Cu2+ By adding cyclodextrin dopamine polymer, the binding force of antimicrobial active substances on the fiber material can be significantly improved, thereby improving the antimicrobial sustainability of the fiber material. At the same time, cyclodextrin dopamine polymer can include antimicrobial active substances to a certain extent, slowly and continuously releasing antimicrobial free radicals or ions to maintain its long-term antimicrobial ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 The figure is a comparison chart of the antibacterial rates of the fiber materials prepared in each embodiment and comparative example;

[0015] Figure 2 The following is a comparison chart of the breaking strength of the fiber materials prepared in various embodiments and comparative examples. DETAILED DESCRIPTION

[0016] The present invention will be further described below with reference to the embodiments.

[0017] Example 1

[0018] A method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the following steps:

[0019] (1) Deionized water was poured into a reactor, and then citric acid, glycine, and urea were added to the deionized water in a ratio of citric acid: glycine: urea: deionized water = 16 g: 2 g: 8 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed and heated to 160° C. for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a relative molecular mass cutoff of 1000 to remove unreacted citric acid, glycine, and urea; the dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0020] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 0.7 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.1 g: 100 mL; after the addition is completed, the solution is heated to 35°C in a water bath, kept warm and stirred for 5 hours, and then the solid and liquid are separated, and the solid phase is dried at 60°C for 3 hours to obtain a cyclodextrin dopamine polymer;

[0021] (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, and the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; after the addition is completed, heating in a water bath to 50° C., stirring at constant temperature for 1 hour, and then separating the solid and liquid, and drying the solid phase at 60° C. for 2 hours to obtain a surface-modified powder;

[0022] (4) The antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 1:1:3:100, and the mass percentage of cellulose in the viscose spinning solution is 9%; after adding the materials, the materials are stirred for 2 hours to mix evenly, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmosphere) to remove bubbles, and then wet-spun and coagulated in a coagulation bath at 45°C to form; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, the fibers are washed with deionized water and dried to obtain the fiber material.

[0023] Example 2

[0024] A method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the following steps:

[0025] (1) Deionized water was poured into a reactor, and then citric acid, glycine, and urea were added to the deionized water in a ratio of citric acid: glycine: urea: deionized water = 17 g: 3 g: 10 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed, heated to 160° C. and kept warm for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a relative molecular mass cutoff of 1000 to remove unreacted citric acid, glycine, and urea; the dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0026] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 0.8 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.1 g: 100 mL; after the addition is completed, heating in a water bath to 35°C, stirring at this temperature for 5 hours, and then separating the solid and liquid, and drying the solid phase at 60°C for 3 hours to obtain a cyclodextrin dopamine polymer;

[0027] (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 4%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, and the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; after the addition is completed, heating in a water bath to 50° C., stirring at constant temperature for 1 hour, and then separating the solid and liquid, and drying the solid phase at 60° C. for 2 hours to obtain a surface-modified powder;

[0028] (4) The antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 1:2:4:100, and the mass percentage of cellulose in the viscose spinning solution is 9%; after adding the materials, the materials are stirred for 2 hours to mix evenly, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmosphere) to remove bubbles, and then wet-spun and coagulated in a coagulation bath at 45°C to form; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, the fibers are washed with deionized water and dried to obtain the fiber material.

[0029] Example 3

[0030] A method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the following steps:

[0031] (1) Deionized water was poured into a reactor, and then citric acid, glycine, and urea were added to the deionized water in a ratio of citric acid: glycine: urea: deionized water = 17 g: 3 g: 10 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed, heated to 160° C. and kept warm for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a relative molecular mass cutoff of 1000 to remove unreacted citric acid, glycine, and urea; the dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0032] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 0.9 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; after the addition is completed, the mixture is heated to 35°C in a water bath, kept warm and stirred for 5 hours, and then solid-liquid separation is performed, and the solid phase is dried at 60°C for 3 hours to obtain a cyclodextrin dopamine polymer;

[0033] (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 4%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, and the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; after the addition is completed, heating in a water bath to 50° C., stirring at constant temperature for 1 hour, and then separating the solid and liquid, and drying the solid phase at 60° C. for 2 hours to obtain a surface-modified powder;

[0034] (4) The antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 2:3:5:100, and the mass percentage of cellulose in the viscose spinning solution is 9%; after adding the materials, the materials are stirred for 2 hours to mix evenly, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmosphere) to remove bubbles, and then wet-spinned, and coagulated in a coagulation bath at 45°C to form; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, the fiber material is washed with deionized water and dried to obtain the fiber material.

[0035] Example 4

[0036] A method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the following steps:

[0037] (1) Deionized water was poured into a reactor, and then citric acid, glycine, and urea were added to the deionized water in a ratio of citric acid: glycine: urea: deionized water = 18 g: 4 g: 12 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed and heated to 160° C. for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a molecular weight cutoff of 1000 to remove unreacted citric acid, glycine, and urea. The dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0038] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 1.0 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; after the addition is completed, heating in a water bath to 35°C, keeping the temperature at 35°C and stirring for 5 hours, then separating the solid and liquid, and drying the solid phase at 60°C for 3 hours to obtain a cyclodextrin dopamine polymer;

[0039] (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 5%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, and the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; after the addition is completed, heating in a water bath to 50° C., stirring at constant temperature for 1 hour, and then separating the solid and liquid, and drying the solid phase at 60° C. for 2 hours to obtain a surface-modified powder;

[0040] (4) The antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 2:5:6:100, and the mass percentage of cellulose in the viscose spinning solution is 9%; after adding the materials, the materials are stirred for 2 hours to mix evenly, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmosphere) to remove bubbles, and then wet-spinned, and coagulated in a coagulation bath at 45°C to form; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, the fibers are washed with deionized water and dried to obtain the fiber material.

[0041] Comparative Example 1

[0042] A comparative method for preparing an antibacterial thermal insulation fiber material for clothing comprises the following steps:

[0043] (1) Deionized water was poured into a reactor, and then citric acid and urea were added to the deionized water in a ratio of citric acid: urea: deionized water = 17 g: 10 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed and heated to 160° C. for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a molecular weight cutoff of 1000 to remove unreacted citric acid and urea. The dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0044] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 0.9 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; after the addition is completed, the mixture is heated to 35°C in a water bath, kept warm and stirred for 5 hours, and then solid-liquid separation is performed, and the solid phase is dried at 60°C for 3 hours to obtain a cyclodextrin dopamine polymer;

[0045] (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 4%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, and the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; after the addition is completed, heating in a water bath to 50° C., stirring at constant temperature for 1 hour, and then separating the solid and liquid, and drying the solid phase at 60° C. for 2 hours to obtain a surface-modified powder;

[0046] (4) The antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution, and the mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 2:3:5:100, and the mass percentage of cellulose in the viscose spinning solution used is 9%; after adding the materials, the mixture is stirred for 2 hours to be evenly mixed, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmospheric pressure) to remove bubbles, and then wet-spun and coagulated in a 45°C coagulation bath to form; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, it is washed with deionized water and dried to obtain the fiber material described in this comparative example.

[0047] Comparative Example 2

[0048] A comparative method for preparing an antibacterial thermal insulation fiber material for clothing comprises the following steps:

[0049] (1) Deionized water was poured into a reactor, and then citric acid, glycine, and urea were added to the deionized water in a ratio of citric acid: glycine: urea: deionized water = 17 g: 3 g: 10 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed, heated to 160° C. and kept warm for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a relative molecular mass cutoff of 1000 to remove unreacted citric acid, glycine, and urea; the dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0050] (2) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 4%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, and the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; after the addition is completed, heating in a water bath to 50° C., stirring at constant temperature for 1 hour, and then separating the solid and liquid, and drying the solid phase at 60° C. for 2 hours to obtain a surface-modified powder;

[0051] (3) The antibacterial matrix powder and the surface modified powder are added to the viscose spinning solution in a mass ratio of antibacterial matrix powder: surface modified powder: viscose spinning solution = 2:5:100, and the mass percentage of cellulose in the viscose spinning solution is 9%; after adding the materials, the materials are stirred for 2 hours to mix evenly, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmospheric pressure) to remove bubbles, and then wet-spun, and coagulated in a coagulation bath at 45°C to form; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, the fibers are washed with deionized water and dried to obtain the fiber material described in this comparative example.

[0052] Comparative Example 3

[0053] A comparative method for preparing an antibacterial thermal insulation fiber material for clothing comprises the following steps:

[0054] (1) Deionized water was poured into a reactor, and then citric acid, glycine, and urea were added to the deionized water in a ratio of citric acid: glycine: urea: deionized water = 17 g: 3 g: 10 g: 100 mL; the mixture was stirred under ultrasonic conditions for 30 min to completely dissolve; the reactor was sealed, heated to 160° C. and kept warm for 3 h; after the insulation was completed, the mixture was naturally cooled to room temperature, the reactor was opened, and the product in the reactor was dialyzed for 12 h in a dialysis membrane with a relative molecular mass cutoff of 1000 to remove unreacted citric acid, glycine, and urea; the dialyzed solution was concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder;

[0055] (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 0.9 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; after the addition is completed, the mixture is heated to 35°C in a water bath, kept warm and stirred for 5 hours, and then solid-liquid separation is performed, and the solid phase is dried at 60°C for 3 hours to obtain a cyclodextrin dopamine polymer;

[0056] (3) The antibacterial matrix powder, cyclodextrin dopamine polymer and copper peroxide powder are added to the viscose spinning solution, and the mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer and copper peroxide powder to the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: copper peroxide powder: viscose spinning solution = 2:3:5:100, and the mass percentage of cellulose in the viscose spinning solution used is 9%; after adding the materials, the mixture is stirred for 2 hours to be evenly mixed, and allowed to stand for 5 hours under a negative pressure environment (0.01 standard atmospheric pressure) to remove bubbles, and then wet-spun and coagulated in a coagulation bath at 45°C; the wet spinning uses a spinneret with an aperture of 70 μm, and the spinneret draft is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, it is washed with deionized water and dried to obtain the fiber material described in this comparative example.

[0057] Example 5

[0058] The antibacterial rates of the fiber materials prepared by the methods described in the above examples and comparative examples were tested according to the requirements of the standard GB / T20944.3-2008 (oscillation method): the fiber materials to be tested were chopped up, steamed and sterilized, and then transferred into the culture medium containing Staphylococcus aureus and cultured under oscillation at 25°C for 24 hours. The cultured bacterial solution was diluted (by 10-fold dilution method, 10-fold and 10-fold respectively) and the antibacterial rates of the fiber materials prepared by the methods described in the above examples and comparative examples were tested. 2 times, 10 3 times, 104 times), diluted and inoculated onto agar plates, cultured at 37°C for 24 h, and the inhibition rate was calculated by counting the number of colonies. The results are as follows Figure 1 In addition, according to the requirements of GB / T14337-2022, the breaking strength of the fiber materials prepared by the methods described in the above embodiments and comparative examples was tested; before the test, the fiber materials to be tested were conditioned at 20°C and 65% humidity for 18 hours; each group of samples was tested 10 times and the average value was taken. The results are shown in the figure. Figure 2 shown.

[0059] Depend on Figure 1 and Figure 2 It can be seen that the fiber material prepared by the method of the present invention has good antibacterial properties and a certain strength, meets the standard requirement of ≥70% antibacterial rate, and improves the pollution resistance and durability of clothing fiber material. By comparing Example 3 and each comparative example, it can be seen that adding the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder prepared by the present invention to traditional fiber material is the key to achieving fiber material antibacterial properties and improving strength, which may be due to: on the fiber material surface load amino acid type carbon quantum dot antibacterial matrix powder of the present invention, on the one hand, the carbon quantum dot surface functional group can interact with the microbial cell membrane, destroying the integrity of the bacterial cell membrane, thereby improving the effect of bactericidal property, while adding glycine can significantly increase the number of amino groups, improve the adhesion strength of antibacterial matrix powder and fiber material. On the other hand, amino acid type carbon quantum dot antibacterial matrix powder can form a carbon layer on the fiber surface, play a role in blocking heat and gas, and improve the warmth retention performance of fiber material. Secondly, surface-modified copper peroxide powder is added to improve the binding force between copper peroxide powder and cyclodextrin dopamine polymer and fiber material. The copper peroxide particles gradually decompose and release hydroxyl radicals (·OH) and Cu 2+ By adding cyclodextrin dopamine polymer, the binding force of antimicrobial active substances on the fiber material can be significantly improved, thereby improving the antimicrobial sustainability of the fiber material. At the same time, cyclodextrin dopamine polymer can include antimicrobial active substances to a certain extent, slowly and continuously releasing antimicrobial free radicals or ions to maintain its long-term antimicrobial ability.

[0060] The technical solutions provided by the present invention are described in detail above. For those skilled in the art, according to the ideas of the embodiments of the present invention, there may be changes in the specific implementation methods and application scopes. In summary, the contents of this specification should not be understood as limiting the present invention.

Claims

1. A method for preparing an antibacterial thermal insulation fiber material for clothing, characterized in that the steps include: (1) Deionized water is poured into a reactor, and then citric acid, glycine, and urea are added to the deionized water and stirred to dissolve under an ultrasonic environment; the reactor is sealed and heated to 150-170°C for hydrothermal insulation; after the insulation is completed, it is naturally cooled to room temperature, and the product is dialyzed in a dialysis membrane to remove unreacted citric acid, glycine, and urea. The dialyzed solution is concentrated under reduced pressure and freeze-dried to obtain an antibacterial matrix powder; (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of the cyclodextrin in the cyclodextrin solution is 0.7-1.0 g / 100 mL; then adding dopamine hydrochloride to the solution under stirring, wherein the amount of dopamine hydrochloride added and the amount of the cyclodextrin solution are dopamine hydrochloride: cyclodextrin solution = 0.1-0.2 g: 100 mL; after the addition is completed, heating in a water bath to 35±5°C, stirring at this temperature for more than 5 hours, and then separating the solid and liquid, and drying the solid phase to obtain a cyclodextrin dopamine polymer; (3) preparing an ethanol solution of γ-aminopropyltriethoxysilane, wherein the mass percentage of γ-aminopropyltriethoxysilane in the ethanol solution is 3% to 5%, and the solvent is ethanol; adding copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, wherein the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50 to 100; after the addition is completed, heating in a water bath to 50±5°C, stirring at a constant temperature for more than 1 hour, and then separating the solid and liquid, and drying the solid phase to obtain a surface-modified powder; (4) adding the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder to the viscose spinning solution, stirring for more than 2 hours to mix the materials evenly, standing under a negative pressure environment to remove bubbles, and then wet spinning and coagulation forming. After forming, washing with deionized water and drying to obtain the fiber material.

2. The method for preparing an antibacterial thermal insulation fiber material for clothing according to claim 1, characterized in that: In the step (1), the citric acid, glycine, and urea are added to deionized water in the following ratio: citric acid: glycine: urea: deionized water = 16-18 g: 2-4 g: 8-12 g: 100 mL; and the hydrothermal insulation time at 150-170° C. is 3-4 h.

3. The method for preparing an antibacterial thermal insulation fiber material for clothing according to claim 1, characterized in that: In the step (2), the concentration of the Tris buffer used is 50 mM, and the pH is 8.

5.

4. The method for preparing an antibacterial thermal insulation fiber material for clothing according to claim 1, characterized in that: In the step (4), the antibacterial matrix powder, cyclodextrin dopamine polymer and surface modified powder are added to the viscose spinning solution in a mass ratio of antibacterial matrix powder: cyclodextrin dopamine polymer: surface modified powder: viscose spinning solution = 1-2:1-5:3-6:100.

Images