A method for preparing colored antibacterial textiles
By treating waste colored cotton fabrics with sulfuric acid hydrolysis and chemical cross-linking, colored antibacterial textiles were prepared, solving the problem that the color of waste cotton fabrics affected their application, and realizing resource utilization and improved antibacterial performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHANGZHOU UNIV
- Filing Date
- 2026-03-20
- Publication Date
- 2026-05-26
AI Technical Summary
The color of waste cotton fabrics affects the subsequent application of cellulose, and existing technologies have failed to effectively utilize waste textile resources.
Waste colored cotton fabrics were treated by sulfuric acid hydrolysis to prepare colored cellulose, which was then fixed onto textiles through cationic modification and chemical crosslinking to form colored antibacterial textiles.
The resource utilization of waste textiles has been realized, and colored textiles with excellent water dispersibility and antibacterial properties have been obtained, with excellent color stability and antibacterial properties.
Smart Images
Figure CN122082243A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of textiles, and specifically relates to a method for preparing colored antibacterial textiles. Background Technology
[0002] With the improvement of people's living standards and the popularization of fast-paced consumption, the life cycle of textiles is becoming shorter and shorter. It is estimated that China generates a total of 26 million tons of waste textiles every year, but the recycling rate is less than 20%. Cotton fiber, as an important textile material, has a very large production and demand. Waste cotton fabrics account for about 24% of the total textile waste generated each year. Therefore, the recycling and reuse of waste cotton textiles is particularly important.
[0003] Waste cotton fabrics are mainly composed of cotton cellulose, making them an ideal raw material for extracting cellulose, especially nanocellulose. The extracted nanocellulose not only retains the basic properties of natural cellulose but also possesses many superior characteristics such as high modulus, high strength, and a large specific surface area. However, the inherent color of waste cotton fabrics can cause the resulting cellulose to exhibit different colors, affecting its subsequent applications. Summary of the Invention
[0004] To overcome the shortcomings of the prior art, the present invention provides a method for preparing colored antibacterial textiles. The method uses waste colored cotton fabrics as raw materials, adopts sulfuric acid hydrolysis to prepare colored cellulose, and after cationic modification, it is then fixed onto the textiles through chemical crosslinking to obtain colored antibacterial textiles.
[0005] The method for preparing colored antibacterial textiles provided by the present invention includes the following steps:
[0006] (1) After cutting the waste colored cotton fabric into pieces, immerse it in sulfuric acid with a mass fraction of 50%-70% at a material-to-liquid ratio of 1:5-1:10 g / mL and acid hydrolyze it at 50-70℃ for 1-3 hours. After the reaction is completed, add water to regenerate it. Centrifuge the degradation product at 4000r / min for 5 minutes, remove the supernatant, wash the bottom gel precipitate with deionized water 6-7 times, disperse it in deionized water, neutralize it with ammonium bicarbonate until no bubbles are generated, centrifuge the neutralized suspension, collect the precipitate, wash it with deionized water 3-5 times to obtain colored cellulose.
[0007] (2) The colored cellulose obtained in step (1) is ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1-6 g / L. A cationic modifier is added, and the pH of the solution is adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution is reacted at 65°C for 120-270 min, centrifuged, and the bottom cationic modified colored cellulose is collected.
[0008] The cationic modifier is 3-chloro-2-hydroxypropyltrimethylammonium chloride, and its mass fraction relative to colored cellulose is 3-5%.
[0009] (3) Take cationic modified colored cellulose and ultrasonically disperse it into 20 mL of deionized water. Add crosslinking agent, then add additives. Stir for 5 min and pour the colored cellulose dispersion into a centrifuge tube. Centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0010] The crosslinking agent is epichlorohydrin, trifunctional aziridine crosslinking agent, or polyethylene glycol glycidyl ether, and the mass ratio of the crosslinking agent (calculated by epoxy or cyclonitro group) to the colored cellulose is 1:4-1:16; the additive is polyethyleneimine or polylysine, and the additive accounts for 3%-8% of the mass of the colored cellulose.
[0011] This invention uses waste colored cotton fabrics as raw materials. By acid hydrolysis to destroy the cellulose macromolecular chains, colored micro / nanocellulose is obtained. After cationic modification, cationic modified colored cellulose with excellent water dispersibility is obtained. Polyethyleneimine or polylysine is then added to change the stability of the cationic modified colored cellulose aqueous dispersion, causing it to flocculate and form a gel. A crosslinking agent is used to form chemical crosslinks between cellulose, polyethyleneimine or polylysine, and the textile substrate to obtain colored antibacterial textiles with excellent performance.
[0012] The beneficial effects of this invention are as follows:
[0013] (1) Waste colored cotton fabrics were used as raw materials to realize the resource utilization of waste textiles.
[0014] (2) Cross-linking is achieved between cationic modified colored cellulose gel, polyethyleneimine or polylysine and textile substrate by using epoxy or cyclonitrogen cross-linking agents to achieve coloring and antibacterial finishing of textiles. Attached Figure Description
[0015] Figure 1 The inhibition zone of the sample obtained in Example 4-1 (where, left: Staphylococcus aureus; right: Escherichia coli).
[0016] Figure 2 The inhibition zone of the sample obtained in Example 4-2 (where, left: Staphylococcus aureus; right: Escherichia coli). Detailed Implementation
[0017] The present invention will now be described in further detail with reference to specific embodiments. It should be understood that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention in any way.
[0018] Example 1
[0019] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0020] (2) The colored cellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored cellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0021] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of crosslinking agent (calculated by epoxy group) to colored cellulose is 1:4. Then add 3% polyethyleneimine relative to the mass of cationic modified colored cellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0022] Example 2
[0023] (1) After cutting up the waste purple cotton fabric, it was immersed in 70% sulfuric acid at a ratio of g / mL to liquid 1:8 and acidified at 50°C for 1 hour. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 min, the supernatant was removed, the bottom gel precipitate was washed 7 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension after centrifugation was collected, the precipitate was washed 5 times with deionized water to obtain colored cellulose.
[0024] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 6 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 5% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The reaction was carried out at 65°C for 270 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0025] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add trifunctional aziridine crosslinking agent. The mass ratio of crosslinking agent (calculated by cyclic nitrogen group) to colored nanocellulose is 1:16. Then add 8% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and dry.
[0026] Example 3
[0027] (1) After cutting the waste yellow cotton fabric into pieces, it was immersed in 60% sulfuric acid at a ratio of g / mL to liquid at 1:5 and acidified at 60℃ for 2 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension was centrifuged, the precipitate was collected, and washed 4 times with deionized water to obtain colored cellulose.
[0028] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 3 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 4% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The reaction was carried out at 65°C for 180 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0029] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent polyethylene glycol glycidyl ether. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:8. Then add 6% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0030] Comparative Example 1-1
[0031] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0032] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0033] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it into 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry it at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap it at 85℃ for 15 min, wash it with hot water at 60℃ for 5 min, wash it with room temperature water for 5 min, and then dry it.
[0034] Comparative Examples 1-2
[0035] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0036] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0037] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it into 20 mL of deionized water. Add 3% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. Stir for 5 min and then pour the colored cellulose dispersion into a centrifuge tube. Centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0038] Comparative Examples 1-3
[0039] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0040] (2) Take 1 g of colored cellulose from step (1) and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. Then add 3% polyethyleneimine relative to the mass of the cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0041] Example 4-1
[0042] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0043] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0044] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. Then add 3% polylysine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0045] Example 4-2
[0046] (1) After cutting the waste purple cotton fabric into pieces, it was immersed in 70% sulfuric acid at a ratio of g / mL to liquid 1:8 and acidified at 50°C for 1 hour. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 min, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension was centrifuged, the precipitate was collected, and washed 5 times with deionized water to obtain colored cellulose.
[0047] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 6 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 5% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 270 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0048] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it into 20 mL of deionized water. Add the trifunctional aziridine crosslinking agent. The mass ratio of the crosslinking agent (calculated by cyclic nitrogen group) to the colored nanocellulose is 1:16. Then add 8% polylysine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0049] Example 4-3
[0050] (1) After cutting the waste yellow cotton fabric into pieces, it was immersed in 60% sulfuric acid at a ratio of g / mL to liquid at 1:5 and acidified at 60℃ for 2 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, neutralized with ammonium bicarbonate until no bubbles were generated, the suspension was centrifuged, the precipitate was collected, and washed 4 times with deionized water to obtain colored cellulose.
[0051] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 3 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 4% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The reaction was carried out at 65°C for 180 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0052] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent polyethylene glycol glycidyl ether. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:8. Then add 6% polylysine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0053] Example 5-1
[0054] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0055] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 1% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0056] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. Then add 3% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0057] Example 5-2
[0058] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0059] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 7% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0060] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. Then add 3% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0061] Example 6-1
[0062] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0063] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0064] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:20. Then add 3% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0065] Example 6-2
[0066] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0067] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0068] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:1. Then add 3% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0069] Example 7-1
[0070] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0071] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0072] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. Then add 1% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0073] Example 7-2
[0074] (1) After cutting the waste red cotton fabric into pieces, it was immersed in 50% sulfuric acid at a material-to-liquid ratio of 1:10 g / mL and acidified at 70℃ for 3 hours. After the reaction was completed, water was added for regeneration. The degradation product was centrifuged at 4000 r / min for 5 minutes, the supernatant was removed, the bottom gel precipitate was washed 6 times with deionized water, dispersed in deionized water, and neutralized with ammonium bicarbonate until no bubbles were generated. The suspension after centrifugation was collected, the precipitate was washed 3 times with deionized water to obtain colored cellulose.
[0075] (2) The colored nanocellulose obtained in step (1) was ultrasonically dispersed in deionized water to prepare a suspension with a concentration of 1 g / L. The cationic modifier 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, with a mass fraction of 3% relative to the colored nanocellulose. The pH of the solution was adjusted to 12 with 4 mol / L sodium hydroxide solution. The solution was reacted at 65°C for 120 min. After centrifugation, the bottom cationic modified colored cellulose was collected.
[0076] (3) Take 1 g of cationic modified colored cellulose and ultrasonically disperse it in 20 mL of deionized water. Add the crosslinking agent epichlorohydrin. The mass ratio of the crosslinking agent (calculated by epoxy group) to the colored nanocellulose is 1:4. Then add 10% polyethyleneimine relative to the mass of cationic modified colored nanocellulose. After stirring for 5 min, pour the colored cellulose dispersion into a centrifuge tube and centrifuge at 4000 r / min for 5 min to remove bubbles. Collect the cationic modified colored cellulose gel at the bottom and use a coating tool to evenly coat it onto the surface of cotton fabric. Dry at 70℃ for 0.5 h. Prepare a 2 g / L soap solution and soap at 85℃ for 15 min, wash with hot water at 60℃ for 5 min, wash with room temperature water for 5 min, and then dry.
[0077] Example 8
[0078] Color parameter test: Fold the dyed fabric in half twice, and use a datacolor tester to measure the K / S value of the cotton fabric under the test conditions of D65 light source and 10° observation angle. Test each sample at different positions 4 times and take the average value.
[0079] According to GB / T 20944.1-2007 "Evaluation of Antimicrobial Properties of Textiles" Part 1: Evaluation Criteria of Agar Plate Diffusion Method, the size of the inhibition zone against Escherichia coli and Staphylococcus aureus was compared between the fabric sample obtained in this invention and the untreated white fabric.
[0080] Table 1
[0081]
[0082] As shown in Table 1, the K / S values of the colored fabrics prepared in Examples 1, 2, 3, 4-1, 4-2, and 4-3, both before and after washing, are significantly higher than those of the corresponding comparative examples. The K / S values of Example 1 before and after washing (5.98 / 5.69) far exceed those of Comparative Example 1 (2.61 / 2.31). The additives polyethyleneimine or polylysine can alter the stability of nanocellulose in aqueous solution, causing it to flocculate and form a gel. Therefore, the dyed fabrics (Examples 1, 2, and 3) with added polyethyleneimine or polylysine are all darker than those of Comparative Example 1 (higher K / S values). Furthermore, the molecular chains of polyethyleneimine or polylysine are rich in amino groups, which, under the action of crosslinking agents, can form a dense three-dimensional crosslinked network with cationic modified cellulose, firmly anchoring the colored components and imparting excellent wash fastness. The changes in K / S values before and after washing in Comparative Examples 1 and 2 illustrate this point. The quaternary ammonium group in the cationic modifier, the amino group in polyethyleneimine, or the amino group in polylysine imparts certain antibacterial properties to the resulting fabric.
Claims
1. A method of making a colored antimicrobial textile, characterized in that: The preparation method comprises the following steps: (1) cutting the waste colored cotton fabric, immersing it in sulfuric acid, regenerating after acidolysis reaction, centrifuging the degradation product, removing the supernatant, washing the bottom gel-like precipitate with deionized water, dispersing it in deionized water, neutralizing it with ammonium bicarbonate until no bubbles are generated, centrifuging the neutralized suspension, collecting the precipitate, and washing it with deionized water to obtain colored cellulose; (2) dispersing the obtained colored cellulose in deionized water to prepare a suspension, adding a cationic modifier, adjusting the pH of the solution to 12 with sodium hydroxide solution, centrifuging and collecting the bottom cationic modified colored cellulose; (3) dispersing the cationic modified colored cellulose in deionized water, adding a crosslinking agent, then adding an additive, stirring, pouring the colored cellulose dispersion into a centrifuge tube, centrifuging to remove bubbles, collecting the bottom cationic modified colored cellulose gel, uniformly coating it onto the surface of the cotton fabric using a film applicator, drying, soaping, washing in hot water at 60℃, and washing in cold water at room temperature to obtain a colored antibacterial textile.
2. The method of making colored antibacterial textiles according to claim 1, characterized in that, In step (1), the ratio of waste colored cotton fabric to sulfuric acid is 1:5-1:10 g / mL, and the mass fraction of sulfuric acid is 50%-70%.
3. The method of making colored antimicrobial textiles according to claim 1, characterized in that, In step (1), the acidolysis temperature is 50-70℃, and the acidolysis time is 1-3h.
4. The method of making colored antimicrobial textiles according to claim 1, characterized in that, In step (2), the concentration of the suspension is 1-6 g / L; the cationic modifier is 3-chloro-2-hydroxypropyltrimethylammonium chloride, and its mass fraction relative to the colored cellulose is 3-5%; the reaction temperature is 65℃, and the reaction time is 120-270 min.
5. The method of making colored antimicrobial textiles according to claim 1, wherein, In step (3), the crosslinking agent is epichlorohydrin, trifunctional aziridine crosslinking agent, or polyethylene glycol glycidyl ether, and the mass ratio of the crosslinking agent (calculated based on epoxy or ring nitrogen group) to the colored cellulose is 1:4-1:
16.
6. The method of making colored antimicrobial textiles of claim 1, wherein, In step (3), the additive is polyethyleneimine or polylysine, and the additive accounts for 3%-8% of the mass of the colored cellulose.
7. The method of making colored antimicrobial textiles according to claim 1, wherein, In step (3), the drying temperature is 70℃, and the drying time is 0.5h; the soaping uses a soap solution with a concentration of 2 g / L, the soaping temperature is 85℃, and the soaping time is 15 min.
8. A colored antibacterial textile prepared by the method according to any one of claims 1-7.