Acrylic fiber yarn with lasting antibacterial and deodorizing functions and preparation process of acrylic fiber yarn

Abstract

The invention relates to the technical field of textile materials, in particular to acrylic fiber yarn with a lasting antibacterial and deodorizing function and a preparation technology of the acrylic fiber yarn. The acrylic fiber yarn with good deodorizing and antibacterial durability is prepared from acrylic textile stock solution, an antibacterial deodorant A and an antibacterial deodorant B; wherein the antibacterial deodorant A can effectively improve the antibacterial property of the acrylic fiber yarn and is easy to degrade after a human body sweats, the pomegranate peel ethanol extract and epsilon-polylysine better show the antibacterial property, growth and reproduction of bacteria are fundamentally inhibited, and generation of odor is prevented; the antibacterial deodorant A and the antibacterial deodorant B which are different in particle size are mixed, so that the antibacterial deodorant A and the antibacterial deodorant B can be quickly released, the aims of quickly deodorizing and resisting bacteria can be fulfilled, the lasting antibacterial and deodorizing effects can be guaranteed, and the acrylic fiber yarn has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of textile materials technology, and in particular to a durable antibacterial and deodorizing acrylic fiber yarn and its preparation process. Background Technology

[0002] Acrylic fiber is the trade name for polypropylene fiber in my country. It usually refers to synthetic fiber made by wet spinning or dry spinning of a copolymer of more than 85% acrylonitrile with the second and third monomers. Because acrylic fiber has excellent softness, warmth, light resistance and radiation resistance, its appearance and properties are very similar to wool, and it is known as "artificial wool". It is an important wool textile material. In the current textile industry, it is usually made into acrylic yarn, acrylic wool or acrylic wool and other wool textile materials, and then spun into acrylic yarn.

[0003] However, due to the strong hydrophobicity of the macromolecular structure of acrylic fibers, they easily absorb organic matter from human sweat and sebum, becoming a breeding ground for microorganisms (such as Staphylococcus aureus, Escherichia coli, Candida albicans, etc.). This results in the fibers producing an unpleasant odor and even causing skin allergies. Consequently, acrylic fibers with deodorizing and antibacterial properties are in high demand in clothing products such as underwear.

[0004] In the existing technology, the research and production of antibacterial and moisture-wicking acrylic fibers and fabrics provides a two-step wet spinning technology for acrylic fibers. This method uses chitosan as an antibacterial additive and NaSCN as a solvent. Post-treatment is carried out during the spinning process. The antibacterial additive is mixed and formulated with acrylic oil and then combined with the fiber in the form of oil. Although the product obtained by this method has excellent antibacterial properties, the process is complex and expensive, and the antibacterial durability needs to be further improved.

[0005] Therefore, based on the relevant technologies mentioned above, there is an urgent need to develop a durable antibacterial and deodorizing acrylic fiber yarn and its preparation process. Summary of the Invention

[0006] In view of this, the purpose of this invention is to propose a durable antibacterial and deodorizing acrylic fiber yarn and its preparation process, so as to solve the problem of poor deodorization and antibacterial durability of acrylic fiber yarn in the prior art.

[0007] To achieve the above objectives, the present invention provides a durable antibacterial and deodorizing acrylic fiber yarn and its preparation process.

[0008] A long-lasting antibacterial and deodorizing acrylic fiber yarn, comprising the following raw materials in parts by weight: Acrylic fiber spinning solution 100-150 parts; antibacterial deodorant A 1.5-2.4 parts; antibacterial deodorant B 3-3.8 parts; The particle size of the antibacterial and deodorizing agent A is 20-25 μm; The particle size of the antibacterial and deodorizing agent B is 1-5 μm; The acrylic fiber spinning solution is prepared from polyacrylonitrile, organic solvent, and modified chitosan solution; The modified chitosan solution was prepared from α-lipoic acid, chitosan, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. The antibacterial and deodorizing agent A was prepared from pomegranate peel ethanol extract, modified sodium alginate and ε-polylysine; The antibacterial and deodorizing agent B is prepared from modified chitosan solution, modified nano-silica and geraniol.

[0009] Preferably, the antibacterial deodorant A is prepared as follows: Step A1. Take pomegranate peel and dry it in an oven at 38-45℃ for 60-65 hours, crush it, and pass it through a 40-mesh sieve to obtain pomegranate peel powder. Extract the pomegranate peel powder with 32%-36% ethanol at 65-70℃ for 65-80 minutes to obtain pomegranate peel ethanol extract. Step A2. Dissolve sodium alginate in a 50% (w / w) aqueous ethanol solution, then add sodium periodate solution, stir in a dark environment at 38-43℃ for 6-7 hours, then add ethylene glycol and stir evenly, dialyze in deionized water for 3-4 days, add silver nitrate solution until no precipitate is formed, freeze dry to obtain modified sodium alginate. Step A3. Add modified sodium alginate and pomegranate peel ethanol extract to deionized water, stir well, then add ε-polylysine, and stir at 32-37℃ for 4-5 hours to obtain the aqueous phase; Step A4. Add Span 80 to the mixture and stir until homogeneous to obtain the oil phase. Add the aqueous phase dropwise to the oil phase and stir at 550-650 rpm for 1-1.5 h. Add calcium chloride and stir at 300-400 rpm for 3-4 h. Centrifuge, wash with petroleum ether and deionized water, and freeze dry to obtain antibacterial deodorant A.

[0010] Preferably, the mass ratio of ethanol to pomegranate peel powder in step A1 is 35-40:1; In step A2, the ratio of sodium periodate to deionized water in the sodium periodate aqueous solution is 2-2.6 g: 20-30 mL. The ratio of sodium alginate, 50% ethanol aqueous solution, sodium periodate aqueous solution and ethylene glycol is 6-8g:120-165mL:24-33mL:5-6mL. The ratio of modified sodium alginate, pomegranate peel ethanol extract, deionized water and ε-polylysine in step A3 is 20-35 mg: 3-4 mg: 1-1.5 mL: 3-4 mg; The molecular weight of the ε-polylysine is 3500-4000 g / mol.

[0011] Preferably, the mixture in step A4 is obtained by mixing liquid paraffin and petroleum ether in a volume ratio of 2-3:1; The ratio of Span 80 to the mixture is 4-5g:40-50mL; The ratio of the aqueous phase, oil phase, and calcium chloride used is 5-8 mL: 40-60 mL: 0.6-0.75 g.

[0012] Preferably, the polyacrylonitrile is prepared from acrylonitrile, vinyl acetate and modified L-arginine; The modified L-arginine is prepared as follows: Sodium bicarbonate and arginine hydrochloride were added to deionized water and stirred in an ice-water bath at 0-5°C for 2-3 hours. Then, methacrylic anhydride aqueous solution was added dropwise, and the pH of the system was adjusted to 9 with ammonia. The mixture was washed with dichloromethane and freeze-dried to obtain modified L-arginine. The ratio of sodium bicarbonate, arginine hydrochloride, deionized water and methacrylic anhydride aqueous solution is 16.8-22g:21-29g:100-130mL:30-40mL; The mass fraction of the aqueous methacrylic anhydride solution is 20%-25%.

[0013] Preferably, the method for preparing the polyacrylonitrile is as follows: Acrylonitrile monomer, vinyl acetate and modified L-arginine were added to dimethyl sulfoxide and stirred until homogeneous. Then azodicarbonamide was added, stirred and heated to react. After the reaction was completed, the mixture was cooled to room temperature to obtain a polymer solution. The solution was then added to deionized water to precipitate for 3-5 hours. After filtration, washing with dichloromethane and drying under reduced pressure, polyacrylonitrile was obtained. The mass ratio of acrylonitrile monomer, vinyl acetate, modified L-arginine, dimethyl sulfoxide, and azodicarbonamide is 1:0.1-0.5:0.01-0.03:4.5-11:0.06-0.09; The volume ratio of the polymer solution to deionized water is 1:3-4; The heating reaction is carried out at a temperature of 75-83℃ for a time of 4-5.5 hours.

[0014] Preferably, the modified chitosan solution is prepared as follows: Add α-lipoic acid and sodium hydroxide to deionized water, stir until homogeneous, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide. Stir for 20-30 min, then add chitosan acetate solution with a concentration of 20-25 g / L and anhydrous ethanol. React at room temperature for 16-18 h while stirring to obtain modified chitosan solution. The ratio of α-lipoic acid, sodium hydroxide, deionized water, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, chitosan acetate solution with a concentration of 20-25 g / L, and anhydrous ethanol is 0.045-0.075 g: 0.01-0.015 g: 15-27 mL: 0.04-0.07 g: 0.025-0.042 g: 45-60 mL: 15-20 mL.

[0015] Preferably, the antibacterial and deodorizing agent B is prepared as follows: Step B1. Add 3-isocyanopropyltriethoxysilane, di-n-butyltin dilaurate and ultraviolet absorber T1130 to acetone, stir evenly, and stir at 40-45℃ for 4-5 hours under nitrogen protection to obtain compound A. Step B2. Mix compound A, tetraethyl orthosilicate and ethanol evenly, and ultrasonically emulsify for 10-15 min to obtain modified nano-silica; Step B3. Add polyoxyethylene octylphenyl ether to deionized water, stir evenly, add geraniol and sonicate for 1-1.5 h, then add modified nano silica, stir at 38-43℃ for 2-2.5 h, then add modified chitosan solution, stir at 45-50℃ for 2-3 h, and adjust the pH of the system to 7 with sodium hydroxide to obtain antibacterial deodorant B.

[0016] Preferably, the ratio of 3-isocyanopropyltriethoxysilane, dibutyltin dilaurate, ultraviolet absorber T1130, and acetone in step B1 is 2.47-3.5g:0.04-0.05g:3.55-4.82g:30-50mL; In step B2, the ratio of compound A, tetraethyl orthosilicate, and ethanol is 3.3-3.9 g: 4.2-4.8 g: 10-20 mL. The ratio of polyoxyethylene octylphenyl ether, deionized water, geraniol, modified nano silica, and modified chitosan solution in step B3 is 0.5-0.7g:40-55g:1-2.2g:3-4.2g:22-28mL.

[0017] A process for preparing a long-lasting antibacterial and deodorizing acrylic fiber yarn includes the following steps: Step S1. Mix polyacrylonitrile, organic solvent B and modified chitosan solution evenly to obtain acrylic fiber spinning solution; Step S2. Add antibacterial deodorant A and antibacterial deodorant B to the acrylic spinning solution, stir evenly, and perform wet spinning to obtain acrylic fiber. Then, through the processes of opening and cleaning cotton, carding, drawing, roving, spinning and winding, a durable antibacterial and deodorizing acrylic fiber yarn is obtained. The organic solvent mentioned in step S1 is any one of dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, and tetrahydrofuran; The mass ratio of the polyacrylonitrile, organic solvent, and modified chitosan solution is 1-2:7-11:2.4-3.

[0018] The beneficial effects of this invention are: This invention provides a durable antibacterial and deodorizing acrylic fiber yarn and its preparation process. The invention prepares an acrylic fiber yarn with good deodorizing and antibacterial durability by reacting acrylic textile dosage with antibacterial deodorant A and antibacterial deodorant B. In antibacterial deodorant A, the polyphenols in pomegranate peel ethanol extract have good antibacterial properties, but are unstable at high temperatures. This invention uses a Schiff base reaction to graft ε-polylysine onto modified sodium alginate, which is then crosslinked with calcium chloride to form a three-dimensional network structure, encapsulating the pomegranate peel ethanol extract within the molecule, thus improving its antibacterial durability. Furthermore, human sweating easily produces lactic acid and free fatty acids, creating a weakly acidic microenvironment within clothing. The dynamic imine bonds in antibacterial deodorant A, prepared via the Schiff base reaction, are unstable and easily hydrolyzed under acidic conditions. Therefore, antibacterial deodorant A degrades more easily after human sweating, allowing the pomegranate peel ethanol extract and ε-polylysine to better exhibit antibacterial properties, fundamentally inhibiting bacterial growth and reproduction and preventing odor production. In antibacterial deodorant B, geraniol is a naturally occurring monoterpene alcohol with good bioactivity in antibacterial and deodorizing properties. After modification with chitosan solution, modified nano-silica, and ultraviolet absorbers, it exhibits long-lasting antibacterial and deodorizing performance. Modified nano-silica effectively enhances the abrasion resistance of antibacterial deodorant B, improving the antibacterial properties of acrylic fiber yarn after multiple washes. The modified chitosan solution acts as a shell structure in the molecule, synergistically working with geraniol. Mixing antibacterial deodorant A and antibacterial deodorant B with different particle sizes allows for rapid release, achieving quick deodorization and antibacterial effects while ensuring long-lasting antibacterial and deodorizing results. Compared with existing technologies, this method has broad application prospects. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0020] The sources and properties of some of the raw materials used in this invention are as follows: Pomegranate peel was purchased from Yangling Runmei Agricultural Development Co., Ltd.; sodium alginate was purchased from Shenzhen Ruijite Biotechnology Co., Ltd.; sodium periodate was purchased from Tianjin Zhiyuan Chemical Reagent Co., Ltd.; ε-polylysine was purchased from Aladdin Reagent Database Co., Ltd.; arginine hydrochloride was purchased from Jingjing Pharmaceutical Co., Ltd.; and α-lipoic acid was purchased from Nantong Kaili Biotechnology Co., Ltd.

[0021] Example 1: A process for preparing a long-lasting antibacterial and deodorizing acrylic fiber yarn, comprising the following steps: S1. Take pomegranate peel and dry it in an oven at 38℃ for 60 hours, crush it, and pass it through a 40-mesh sieve to obtain pomegranate peel powder. Extract 1g of pomegranate peel powder with 35g of 32% ethanol at 65℃ for 65 minutes to obtain pomegranate peel ethanol extract. S2. Dissolve 6g of sodium alginate in 120mL of 50% ethanol aqueous solution, then add 24mL of sodium periodate aqueous solution, wherein the ratio of sodium periodate to deionized water is 2g:20mL. Stir for 6h in a dark environment at 38℃, then add 5mL of ethylene glycol and stir evenly. Dialyze in deionized water for 3 days, add silver nitrate solution until no precipitate is formed, freeze dry to obtain modified sodium alginate; S3. Add 20 mg of modified sodium alginate and 3 mg of pomegranate peel ethanol extract to 1 mL of deionized water, stir well, then add 3 mg of ε-polylysine, and stir at 32 °C for 4 h to obtain the aqueous phase; S4. Add 4g of Span 80 to 40mL of a mixture, which is obtained by mixing liquid paraffin and petroleum ether in a volume ratio of 2:1. Stir until homogeneous to obtain an oil phase. Add 5mL of the aqueous phase to the 40mL oil phase. Stir at 550rpm for 1h, then add 0.6g of calcium chloride and stir at 300rpm for 3h. Centrifuge, wash with petroleum ether and deionized water, and freeze dry to obtain antibacterial deodorant A. S5. Add 16.8g sodium bicarbonate and 21g arginine hydrochloride to 100mL deionized water, stir for 2h in an ice-water bath at 0℃, then add 30mL of 20% methacrylic anhydride aqueous solution, adjust the pH of the system to 9 with ammonia, wash with dichloromethane, and freeze dry to obtain modified L-arginine. S6. Add 1g of acrylonitrile monomer, 0.1g of vinyl acetate and 0.01g of modified L-arginine to 4.5g of dimethyl sulfoxide, stir evenly, then add 0.06g of azodicarbonamide, stir and heat at 75℃ for 4h. After the reaction is completed, cool to room temperature to obtain a polymer solution, add 3mL of deionized water to 1mL of polymer solution and let it settle for 3h, filter, wash with dichloromethane, and dry under reduced pressure to obtain polyacrylonitrile; S7. Add 0.045g of α-lipoic acid and 0.01g of sodium hydroxide to 15mL of deionized water, stir well, then add 0.04g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.025g of N-hydroxysuccinimide, stir for 20min, then add 45mL of chitosan acetate solution with a concentration of 20g / L and 15mL of anhydrous ethanol, and react at room temperature for 16h while stirring to obtain modified chitosan solution; S8. Add 2.47g of 3-isocyanopropyltriethoxysilane, 0.04g of di-n-butyltin dilaurate and 3.55g of ultraviolet absorber T1130 to 30mL of acetone, stir evenly, and stir at 40℃ for 4h under nitrogen protection to obtain compound A. S9. Mix 3.3g of compound A, 4.2g of tetraethyl orthosilicate and 10mL of ethanol evenly, and ultrasonically emulsify for 10min to obtain modified nano-silica; S10. Add 0.5g of polyoxyethylene octylphenyl ether to 4g of deionized water, stir evenly, add 1g of geraniol and sonicate for 1h, then add 3g of modified nano silica, stir at 38℃ for 2h, then add 22mL of modified chitosan solution, stir at 45℃ for 2h, and adjust the pH of the system to 7 with sodium hydroxide to obtain antibacterial deodorant B; S11. Mix 1g of polyacrylonitrile, 7g of organic solvent and 2.4g of modified chitosan solution evenly to obtain acrylic fiber spinning solution; S12. Add 1.5g of antibacterial and deodorizing agent A and 3g of antibacterial and deodorizing agent B to 100g of acrylic spinning solution, stir evenly, and perform wet spinning to obtain acrylic fiber. Then, through opening and cleaning, carding, drawing, roving, spinning and winding processes, obtain acrylic fiber yarn with long-lasting antibacterial and deodorizing function.

[0022] Example 2: A process for preparing a long-lasting antibacterial and deodorizing acrylic fiber yarn, comprising the following steps: S1. Take pomegranate peel and dry it in an oven at 40℃ for 63 hours, crush it, and pass it through a 40-mesh sieve to obtain pomegranate peel powder. Extract 1g of pomegranate peel powder with 38g of 34% ethanol at 68℃ for 75 minutes to obtain pomegranate peel ethanol extract. S2. Dissolve 7g of sodium alginate in 142mL of 50% ethanol aqueous solution, then add 28mL of sodium periodate aqueous solution, wherein the ratio of sodium periodate to deionized water is 2.3g:25mL. Stir in a dark environment at 40℃ for 6.5h, then add 5.5mL of ethylene glycol and stir evenly. Dialyze in deionized water for 3 days, add silver nitrate solution until no precipitate is formed, freeze dry to obtain modified sodium alginate; S3. Add 27 mg of modified sodium alginate and 3.5 mg of pomegranate peel ethanol extract to 1.3 mL of deionized water, stir well, then add 3.5 mg of ε-polylysine, and stir at 35 °C for 4.5 h to obtain the aqueous phase; S4. Add 4.5g of Span 80 to 45mL of a mixture, which is obtained by mixing liquid paraffin and petroleum ether at a volume ratio of 2.5:1. Stir until homogeneous to obtain an oil phase. Add 6.5mL of the aqueous phase to 50mL of the oil phase. Stir at 600rpm for 1h, then add 0.67g of calcium chloride and stir at 350rpm for 3.5h. Centrifuge, wash with petroleum ether and deionized water, and freeze dry to obtain antibacterial deodorant A. S5. Add 19g sodium bicarbonate and 25g arginine hydrochloride to 115mL of deionized water, stir for 2.5h in an ice-water bath at 3℃, then add 35mL of 23% methacrylic anhydride aqueous solution, adjust the pH of the system to 9 with ammonia, wash with dichloromethane, and freeze dry to obtain modified L-arginine. S6. Add 1g of acrylonitrile monomer, 0.3g of vinyl acetate and 0.02g of modified L-arginine to 8g of dimethyl sulfoxide, stir evenly, then add 0.075g of azodicarbonamide, stir and heat at 80℃ for 5h. After the reaction is completed, cool to room temperature to obtain a polymer solution, add 3.5mL of deionized water to 1mL of polymer solution and let it settle for 4h, filter, wash with dichloromethane, and dry under reduced pressure to obtain polyacrylonitrile; S7. Add 0.06g α-lipoic acid and 0.013g sodium hydroxide to 21mL deionized water, stir well, then add 0.055g 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.034g N-hydroxysuccinimide, stir for 25min, then add 52mL of chitosan acetate solution with a concentration of 23g / L and 18mL of anhydrous ethanol, and react at room temperature for 17h while stirring to obtain modified chitosan solution; S8. Add 3g of 3-isocyanopropyltriethoxysilane, 0.045g of di-n-butyltin dilaurate and 4.2g of ultraviolet absorber T1130 to 40mL of acetone, stir evenly, and stir at 43℃ for 4.5h under nitrogen protection to obtain compound A; S9. Mix 3.6g of compound A, 4.5g of tetraethyl orthosilicate and 15mL of ethanol evenly, and ultrasonically emulsify for 13min to obtain modified nano-silica; S10. Add 0.6g of polyoxyethylene octylphenyl ether to 47g of deionized water, stir evenly, add 1.6g of geraniol and sonicate for 1.5h, then add 3.6g of modified nano silica, stir at 40℃ for 2.5h, then add 25mL of modified chitosan solution, stir at 48℃ for 2.5h, and adjust the pH of the system to 7 with sodium hydroxide to obtain antibacterial deodorant B; S11. Mix 1.5g of polyacrylonitrile, 9g of organic solvent and 2.7g of modified chitosan solution evenly to obtain acrylic fiber spinning solution; S12. Add 1.9g of antibacterial and deodorizing agent A and 3.4g of antibacterial and deodorizing agent B to 127g of acrylic spinning solution, stir evenly, and perform wet spinning to obtain acrylic fiber. Then, through opening and cleaning, carding, drawing, roving, spinning and winding processes, obtain acrylic fiber yarn with long-lasting antibacterial and deodorizing function.

[0023] Example 3: A process for preparing a long-lasting antibacterial and deodorizing acrylic fiber yarn, comprising the following steps: S1. Take pomegranate peel and dry it in an oven at 45℃ for 65 hours, crush it, and pass it through a 40-mesh sieve to obtain pomegranate peel powder. Extract 1g of pomegranate peel powder with 40g of 36% ethanol at 70℃ for 80 minutes to obtain pomegranate peel ethanol extract. S2. Dissolve 8g of sodium alginate in 165mL of 50% ethanol aqueous solution, then add 33mL of sodium periodate aqueous solution, wherein the ratio of sodium periodate to deionized water is 2.6g:30mL. Stir in a dark environment at 43℃ for 7h, then add 6mL of ethylene glycol and stir evenly. Dialyze in deionized water for 4 days, add silver nitrate solution until no precipitate is formed, freeze dry to obtain modified sodium alginate; S3. Add 35 mg of modified sodium alginate and 4 mg of pomegranate peel ethanol extract to 1.5 mL of deionized water, stir well, then add 4 mg of ε-polylysine, and stir at 37 °C for 5 h to obtain the aqueous phase; S4. Add 5g of Span 80 to 50mL of a mixture, which is obtained by mixing liquid paraffin and petroleum ether in a volume ratio of 3:1. Stir until homogeneous to obtain an oil phase. Add 8mL of the aqueous phase to 60mL of the oil phase. Stir at 650rpm for 1.5h, then add 0.75g of calcium chloride and stir at 400rpm for 4h. Centrifuge, wash with petroleum ether and deionized water, and freeze dry to obtain antibacterial deodorant A. S5. Add 22g sodium bicarbonate and 29g arginine hydrochloride to 130mL deionized water, stir for 3h in an ice-water bath at 5℃, then add 40mL of 25% methacrylic anhydride aqueous solution, adjust the pH of the system to 9 with ammonia, wash with dichloromethane, and freeze dry to obtain modified L-arginine. S6. Add 1g of acrylonitrile monomer, 0.5g of vinyl acetate and 0.03g of modified L-arginine to 11g of dimethyl sulfoxide, stir evenly, then add 0.09g of azodicarbonamide, stir and heat at 83℃ for 5.5h. After the reaction is completed, cool to room temperature to obtain a polymer solution, add 4mL of deionized water to 1mL of polymer solution and let it settle for 5h, filter, wash with dichloromethane and dry under reduced pressure to obtain polyacrylonitrile; S7. Add 0.075g of α-lipoic acid and 0.015g of sodium hydroxide to 27mL of deionized water, stir well, then add 0.07g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.042g of N-hydroxysuccinimide, stir for 30min, then add 60mL of chitosan acetate solution with a concentration of 25g / L and 20mL of anhydrous ethanol, and react at room temperature for 18h while stirring to obtain modified chitosan solution; S8. Add 3.5g of 3-isocyanopropyltriethoxysilane, 0.05g of di-n-butyltin dilaurate and 4.82g of ultraviolet absorber T1130 to 50mL of acetone, stir evenly, and stir at 45℃ for 5h under nitrogen protection to obtain compound A. S9. Mix 3.9g of compound A, 4.8g of tetraethyl orthosilicate and 20mL of ethanol evenly, and ultrasonically emulsify for 15min to obtain modified nano-silica; S10. Add 0.7g of polyoxyethylene octylphenyl ether to 55g of deionized water, stir evenly, add 2.2g of geraniol and sonicate for 1.5h, then add 4.2g of modified nano silica, stir at 43℃ for 2.5h, then add 28mL of modified chitosan solution, stir at 50℃ for 3h, and adjust the pH of the system to 7 with sodium hydroxide to obtain antibacterial deodorant B; S11. Mix 2g of polyacrylonitrile, 11g of organic solvent and 3g of modified chitosan solution evenly to obtain acrylic fiber spinning solution; S12. Add 2.4g of antibacterial and deodorizing agent A and 3.8g of antibacterial and deodorizing agent B to 150g of acrylic spinning solution, stir evenly, and perform wet spinning to obtain acrylic fiber. Then, through opening and cleaning, carding, drawing, roving, spinning and winding processes, obtain acrylic fiber yarn with long-lasting antibacterial and deodorizing function.

[0024] Comparative Example 1: Compared with Example 1, this comparative example did not add antibacterial and deodorizing agent A during the preparation of acrylic fiber yarn. All other steps and parameters were the same, and will not be repeated here. Finally, acrylic fiber yarn was obtained.

[0025] Comparative Example 2: Compared with Example 1, this comparative example did not add antibacterial and deodorizing agent B during the preparation of acrylic fiber yarn. All other steps and parameters were the same, and will not be repeated here. Finally, acrylic fiber yarn was obtained.

[0026] Comparative Example 3: Compared with Example 1, this comparative example did not add modified chitosan solution during the preparation of acrylic textile dope. All other steps and parameters were the same, and will not be repeated here. Finally, acrylic fiber yarn was obtained.

[0027] Comparative Example 4: Compared with Example 1, this comparative example did not add ε-polylysine during the preparation of antibacterial deodorant A. All other steps and parameters were the same, and will not be repeated here. Finally, acrylic fiber yarn was obtained.

[0028] Comparative Example 5: Compared with Example 1, this comparative example only replaces "modified chitosan solution" with "chitosan acetate solution". All other steps and parameters are the same, and will not be repeated here. Finally, acrylic fiber yarn is obtained.

[0029] Comparative Example 6: This comparative example differs from Example 1 only in that "modified L-arginine" is replaced with "itaconic acid". All other steps and parameters are the same, and will not be repeated here. The final product is acrylic fiber yarn.

[0030] Comparative Example 7: Compared with Example 1, this comparative example only replaces "1.5g antibacterial deodorant A and 3g antibacterial deodorant B" with "1.5g antibacterial deodorant A and 9g antibacterial deodorant B". All other steps and parameters are the same, and will not be repeated in this comparative example. Finally, acrylic fiber yarn is obtained.

[0031] Comparative Example 8: Compared with Example 1, this comparative example only replaces "1.5g antibacterial deodorant A and 3g antibacterial deodorant B" with "9g antibacterial deodorant A and 3g antibacterial deodorant B". All other steps and parameters are the same, and will not be repeated in this comparative example. Finally, acrylic fiber yarn is obtained.

[0032] Performance testing: Antibacterial performance test: Referring to the GB / T20944.3-2008 testing standard, Escherichia coli and Staphylococcus aureus were selected as the experimental bacterial strains. The antibacterial properties of the acrylic fiber yarns prepared in Examples 1-3 and Comparative Examples 1-8 were tested, and the antibacterial rates against Escherichia coli and Staphylococcus aureus were recorded as X1 and Y1, respectively. Then, the antibacterial properties of the acrylic fiber yarns prepared in Examples 1-3 and Comparative Examples 1-8 after being washed 100 times were tested, and the antibacterial rates against Escherichia coli and Staphylococcus aureus were recorded as X2 and Y2, respectively. Deodorization performance test: The acrylic fiber yarns prepared in Examples 1-3 and Comparative Examples 1-8 were woven into fabrics and tested, as follows: 10 mL of ammonia water was measured and diluted 1000 times and poured into a container. 2 g of sodium hydroxide was weighed and added to a container containing ammonia water. The container was then quickly placed in a sealed glass container and allowed to evaporate for 1 hour to simulate odor. The concentration of ammonia in the glass container after 1 hour of evaporation was tested using a JC-5 type eight-in-one indoor air detector and recorded as C. Fabrics of uniform length and width of 15 cm were cut and placed into sealed glass containers. A standard light source box was used to simulate sunlight (color temperature 6500 K, power 18 W) to simulate sunlight treatment on the sealed glass containers for 12, 24, and 36 hours, respectively. The concentration of ammonia in the sealed glass container was tested at each time point, and the concentration of ammonia in the sealed glass container after sunlight treatment was recorded as C'. The degradation rate of ammonia was calculated using the following formula to characterize the deodorization rate of the fabric. W= ×100% In the formula: W represents the degradation rate of ammonia in the sealed glass container before and after sunlight treatment, in percentages (%); C represents the ammonia concentration in the glass container before the fabric is placed inside, in mg / m³. 3 C' represents the ammonia concentration inside the sealed glass container after sunlight treatment, in mg / m³. 3 .

[0033] Table 1 Summary of experimental data from Examples 1-3 and Comparative Examples 1-8 Table 2 Summary of experimental data from Examples 1-3 and Comparative Examples 1-8 Data Analysis: As can be seen from Tables 1 and 2, the acrylic fiber yarn prepared by this invention has durable antibacterial and deodorizing properties. This may be because the acrylic spinning solution is prepared from polyacrylonitrile, organic solvent, and modified chitosan solution. Chitosan molecules contain positively charged amino groups, which can react with the negatively charged cell membranes of bacteria, thereby affecting the normal physiological activities of bacteria and leading to their death. Furthermore, through the dehydration condensation reaction between the amino groups on chitosan and the carboxyl groups on α-lipoic acid, lipoic acid is grafted onto chitosan, introducing disulfide bonds into the chitosan. This dynamic covalent bond can effectively improve the properties of the acrylic fiber yarn. Mechanical properties: α-Lipoic acid can cause cell membrane dysfunction, thereby affecting cell morphology changes, and works synergistically with chitosan to exert antibacterial effects; Polyacrylonitrile is prepared from acrylonitrile, vinyl acetate, and modified L-arginine, and guanidine groups with antibacterial properties are introduced into the polyacrylonitrile, which can be firmly bound to the acrylic fiber to achieve long-lasting antibacterial effect; In antibacterial deodorant A, the polyphenols in pomegranate peel ethanol extract have good antibacterial properties, but are unstable at high temperatures. On the one hand, this invention grafts ε-polylysine onto modified sodium alginate through Schiff base reaction, and then crosslinks it with calcium chloride to form a three-dimensional network. The structure of the pomegranate peel ethanol extract is encapsulated within the molecule, enhancing its antibacterial durability. On the other hand, human sweating easily produces lactic acid and free fatty acids, creating a weakly acidic microenvironment within clothing. The dynamic imine bonds in antibacterial deodorant A, prepared via the Schiff base reaction, are unstable and easily hydrolyzed under acidic conditions. Consequently, antibacterial deodorant A degrades more readily after sweating. The pomegranate peel ethanol extract and ε-polylysine exhibit better antibacterial properties, fundamentally inhibiting bacterial growth and reproduction, and preventing odor production. In antibacterial deodorant B, geraniol is a naturally occurring monoterpene alcohol. It exhibits excellent bioactivity in antibacterial and deodorizing properties. After modification with modified chitosan solution, modified nano-silica, and ultraviolet absorbers, it possesses long-lasting antibacterial and deodorizing performance. Among these modifications, the modified nano-silica effectively enhances the abrasion resistance of antibacterial deodorant B, thereby improving the antibacterial properties of acrylic fiber yarn after multiple washes. The modified chitosan solution acts as a shell structure in the molecule and works synergistically with geraniol. By mixing antibacterial deodorant A and antibacterial deodorant B with different particle sizes, it can achieve rapid release, quickly deodorize and antibacterial effects, and also ensure long-lasting antibacterial and deodorizing effects.

[0034] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

[0035] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A long-lasting antibacterial and deodorizing acrylic fiber yarn, characterized in that, Includes the following quantities of raw materials: Acrylic fiber spinning solution 100-150 parts; antibacterial deodorant A 1.5-2.4 parts; antibacterial deodorant B 3-3.8 parts; The particle size of the antibacterial and deodorizing agent A is 20-25 μm; The particle size of the antibacterial and deodorizing agent B is 1-5 μm; The acrylic fiber spinning solution is prepared from polyacrylonitrile, organic solvent, and modified chitosan solution; The modified chitosan solution was prepared from α-lipoic acid, chitosan, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. The antibacterial and deodorizing agent A was prepared from pomegranate peel ethanol extract, modified sodium alginate and ε-polylysine; The antibacterial and deodorizing agent B is prepared from modified chitosan solution, modified nano-silica, and geraniol.

2. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 1, characterized in that, The preparation method of the antibacterial and deodorizing agent A is as follows: Step A1. Take pomegranate peel and dry it in an oven at 38-45℃ for 60-65 hours, crush it, and pass it through a 40-mesh sieve to obtain pomegranate peel powder. Extract the pomegranate peel powder with 32%-36% ethanol at 65-70℃ for 65-80 minutes to obtain pomegranate peel ethanol extract. Step A2. Dissolve sodium alginate in a 50% (w / w) aqueous ethanol solution, then add sodium periodate solution, stir in a dark environment at 38-43℃ for 6-7 hours, then add ethylene glycol and stir evenly, dialyze in deionized water for 3-4 days, add silver nitrate solution until no precipitate is formed, freeze dry to obtain modified sodium alginate. Step A3. Add modified sodium alginate and pomegranate peel ethanol extract to deionized water, stir well, then add ε-polylysine, and stir at 32-37℃ for 4-5 hours to obtain the aqueous phase; Step A4. Add Span 80 to the mixture and stir until homogeneous to obtain the oil phase. Add the aqueous phase dropwise to the oil phase and stir at 550-650 rpm for 1-1.5 h. Add calcium chloride and stir at 300-400 rpm for 3-4 h. Centrifuge, wash with petroleum ether and deionized water, and freeze dry to obtain antibacterial deodorant A.

3. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 2, characterized in that, The mass ratio of ethanol to pomegranate peel powder in step A1 is 35-40:1; In step A2, the ratio of sodium periodate to deionized water in the sodium periodate aqueous solution is 2-2.6 g: 20-30 mL. The ratio of sodium alginate, 50% ethanol aqueous solution, sodium periodate aqueous solution and ethylene glycol is 6-8g:120-165mL:24-33mL:5-6mL. The ratio of modified sodium alginate, pomegranate peel ethanol extract, deionized water and ε-polylysine in step A3 is 20-35 mg: 3-4 mg: 1-1.5 mL: 3-4 mg; The molecular weight of the ε-polylysine is 3500-4000 g / mol.

4. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 2, characterized in that, The mixture described in step A4 is obtained by mixing liquid paraffin and petroleum ether at a volume ratio of 2-3:1; The ratio of Span 80 to the mixture is 4-5g:40-50mL; The ratio of the aqueous phase, oil phase, and calcium chloride used is 5-8 mL: 40-60 mL: 0.6-0.75 g.

5. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 1, characterized in that, The polyacrylonitrile is prepared from acrylonitrile, vinyl acetate and modified L-arginine; The modified L-arginine is prepared as follows: Sodium bicarbonate and arginine hydrochloride were added to deionized water and stirred in an ice-water bath at 0-5°C for 2-3 hours. Then, methacrylic anhydride aqueous solution was added dropwise, and the pH of the system was adjusted to 9 with ammonia. The mixture was washed with dichloromethane and freeze-dried to obtain modified L-arginine. The ratio of sodium bicarbonate, arginine hydrochloride, deionized water and methacrylic anhydride aqueous solution is 16.8-22g:21-29g:100-130mL:30-40mL; The mass fraction of the aqueous methacrylic anhydride solution is 20%-25%.

6. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 1, characterized in that, The preparation method of the polyacrylonitrile is as follows: Acrylonitrile monomer, vinyl acetate and modified L-arginine were added to dimethyl sulfoxide and stirred until homogeneous. Then azodicarbonamide was added, stirred and heated to react. After the reaction was completed, the mixture was cooled to room temperature to obtain a polymer solution. The solution was then added to deionized water to precipitate for 3-5 hours. After filtration, washing with dichloromethane and drying under reduced pressure, polyacrylonitrile was obtained. The mass ratio of acrylonitrile monomer, vinyl acetate, modified L-arginine, dimethyl sulfoxide, and azodicarbonamide is 1:0.1-0.5:0.01-0.03:4.5-11:0.06-0.09; The volume ratio of the polymer solution to deionized water is 1:3-4; The heating reaction is carried out at a temperature of 75-83℃ for a time of 4-5.5 hours.

7. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 1, characterized in that, The modified chitosan solution is prepared as follows: Add α-lipoic acid and sodium hydroxide to deionized water, stir until homogeneous, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide. Stir for 20-30 min, then add chitosan acetate solution with a concentration of 20-25 g / L and anhydrous ethanol. React at room temperature for 16-18 h while stirring to obtain modified chitosan solution. The ratio of α-lipoic acid, sodium hydroxide, deionized water, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, chitosan acetate solution with a concentration of 20-25 g / L, and anhydrous ethanol is 0.045-0.075 g: 0.01-0.015 g: 15-27 mL: 0.04-0.07 g: 0.025-0.042 g: 45-60 mL: 15-20 mL.

8. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 1, characterized in that, The preparation method of the antibacterial and deodorizing agent B is as follows: Step B1. Add 3-isocyanopropyltriethoxysilane, di-n-butyltin dilaurate and ultraviolet absorber T1130 to acetone, stir evenly, and stir at 40-45℃ for 4-5 hours under nitrogen protection to obtain compound A. Step B2. Mix compound A, tetraethyl orthosilicate and ethanol evenly, and ultrasonically emulsify for 10-15 min to obtain modified nano-silica; Step B3. Add polyoxyethylene octylphenyl ether to deionized water, stir evenly, add geraniol and sonicate for 1-1.5 h, then add modified nano silica, stir at 38-43℃ for 2-2.5 h, then add modified chitosan solution, stir at 45-50℃ for 2-3 h, and adjust the pH of the system to 7 with sodium hydroxide to obtain antibacterial deodorant B.

9. The durable antibacterial and deodorizing acrylic fiber yarn according to claim 8, characterized in that, The ratio of 3-isocyanopropyltriethoxysilane, dibutyltin dilaurate, ultraviolet absorber T1130, and acetone used in step B1 is 2.47-3.5g:0.04-0.05g:3.55-4.82g:30-50mL; In step B2, the ratio of compound A, tetraethyl orthosilicate, and ethanol is 3.3-3.9 g: 4.2-4.8 g: 10-20 mL. The ratio of polyoxyethylene octylphenyl ether, deionized water, geraniol, modified nano silica, and modified chitosan solution in step B3 is 0.5-0.7g:40-55g:1-2.2g:3-4.2g:22-28mL.

10. The preparation process of the long-lasting antibacterial and deodorizing acrylic fiber yarn according to any one of claims 1-9, characterized in that, Includes the following steps: Step S1. Mix polyacrylonitrile, organic solvent and modified chitosan solution evenly to obtain acrylic fiber spinning solution; Step S2. Add antibacterial deodorant A and antibacterial deodorant B to the acrylic spinning solution, stir evenly, and perform wet spinning to obtain acrylic fiber. Then, through the processes of opening and cleaning cotton, carding, drawing, roving, spinning and winding, a durable antibacterial and deodorizing acrylic fiber yarn is obtained. The organic solvent mentioned in step S1 is any one of dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, and tetrahydrofuran; The mass ratio of the polyacrylonitrile, organic solvent, and modified chitosan solution is 1-2:7-11:2.4-3.

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