Environment-friendly antibacterial plant-based fabric and preparation method thereof

Abstract

The invention discloses an environment-friendly antibacterial plant-based fabric and a preparation method thereof, and belongs to the technical field of textiles. The environment-friendly antibacterial plant-based fabric is obtained by blending and weaving mint fibers, modal fibers and anti-mosquito linen fibers, the anti-mosquito linen fiber is prepared from the following raw material components: a wormwood extracting solution, modified aluminum nitride, a dispersing agent and linen fiber, wherein the modified aluminum nitride is obtained by coating modified aluminum nitride with a polysiloxane coupling agent; the polysilane coupling agent is obtained by polymerizing furfural disiloxane and hydroxyl polyethylene glycol triethoxy silane; the dispersing agent is obtained by mixing and reacting coconut oil, 3-dimethylaminopropylamine, 2-hydroxy-4-aminoacetophenone and aluminoacetic acid.

Description

Technical Field

[0001] The invention relates to an environmentally friendly antibacterial plant-based fabric and a preparation method thereof. Background Art

[0002] With growing environmental awareness and a pursuit of a healthy and comfortable lifestyle, consumers are increasingly demanding functional fabrics. This is especially true for summer clothing, where consumers demand not only breathable and cooling fabrics but also additional features like insect repellency and antibacterial properties, while maintaining excellent mechanical properties and environmental attributes. However, traditional single-fiber fabrics, due to their inherent structural and performance limitations, often struggle to meet these multi-dimensional functional requirements.

[0003] For example, while ordinary flax fiber has natural antibacterial properties and good breathability, its rough surface makes it prone to itching when worn, and it lacks mosquito repellent properties, limiting its use in high-end summer clothing. On the other hand, mint fiber, due to its natural cooling properties, releases cooling substances upon contact with the skin, providing an immediate cooling effect. However, its fiber strength is relatively low, and its abrasion resistance and mechanical support are poor, which affects its durability in actual use. Furthermore, modal fiber is popular in the market for its excellent skin-friendliness and elasticity, but its antibacterial properties rely on a post-processing chemical additive process, which not only increases the risk of environmental pollution but also reduces the overall environmental attributes of the product.

[0004] Therefore, the applicant developed an environmentally friendly antibacterial fabric based on plant-based fibers, aiming to achieve a synergistic improvement in the cool feeling, mosquito repellency, antibacterial and mechanical properties of the fabric. Summary of the Invention

[0005] The purpose of the present invention is to provide an environmentally friendly antibacterial plant-based fabric and a preparation method thereof, so as to solve the technical problems mentioned in the above background technology.

[0006] The technical solution for achieving the purpose of the present invention is: In a first aspect, the present invention provides an environmentally friendly antibacterial plant-based fabric, which is woven by blending mint fiber, modal fiber, and anti-mosquito and insect repellent flax fiber; the raw material components of the anti-mosquito and insect repellent flax fiber include mugwort extract, modified aluminum nitride, a dispersant, and flax fiber.

[0007] Furthermore, the modified aluminum nitride is obtained by coating modified aluminum nitride with a polysiloxane coupling agent.

[0008] Furthermore, the polysilane coupling agent is obtained by polymerization of furfural disiloxane and hydroxypolyethylene glycol triethoxysilane.

[0009] Furthermore, the dispersant is obtained by mixing coconut oil, 3-dimethylaminopropylamine, 2-hydroxy-4-aminoacetophenone and aluminum acetic acid.

[0010] In a second aspect, the present invention provides a method for preparing the environmentally friendly antibacterial plant-based fabric as described in the first aspect, comprising the following preparation steps: blending and weaving mint fiber, modal fiber, and anti-mosquito and insect repellent flax fiber to obtain the environmentally friendly antibacterial plant-based fabric.

[0011] Furthermore, the preparation method of the mosquito-proof flax fiber is as follows: (1) 4-6 parts by weight of dispersant were placed in a reaction vessel and stirred at 78-82°C for 55-65 minutes, followed by adding 0.25 parts by weight of flax fiber and continuing to stir at 78-82°C until the flax fiber was dissolved. Then, 15-16 parts by weight of dimethyl sulfoxide were added and continued to stir at 78-82°C for 2.5-3.5 hours. Then, 0.12-0.13 parts by weight of modified aluminum nitride were added and continued to stir at 78-82°C for 25-35 minutes. Then, 0.007-0.009 parts by weight of wormwood extract were added and mixed at 25°C for 25-35 minutes to obtain a spinning solution. (2) the spinning solution obtained in step (1) was placed in a drying oven at 38-42°C for 11.5-12.5 hours for degassing; (3) The treated product in step (2) is loaded into a syringe and spun using a spinning machine. The spinning solution is squeezed into a coagulation bath of a mixed solution of 25% sodium hydroxide aqueous solution and ethanol in a volume ratio of 1:9-11 at a speed of 25-35 mm / h. The coagulation time is 6 hours. The product is then washed with deionized water 2-4 times and dried in a drying oven at 60°C for 6 hours to obtain mosquito-proof flax fiber.

[0012] Furthermore, the preparation method of the modified aluminum nitride is as follows: Pour the nano-aluminum nitride powder into a three-necked flask, use anhydrous ethanol 100 times the mass of the nano-aluminum nitride powder as the reaction solvent, heat in a water bath and add a polysilane coupling agent 0.04~0.06 times the mass of the nano-aluminum nitride powder under high-speed stirring, control the temperature to be constant at 54~56°C for constant temperature reaction for 2.5~3.5h, take out, vacuum dry in a vacuum drying oven at 48~52°C for 9.5~10.5h, grind and sieve after taking out, then use acetone as solvent for Soxhlet extraction for 24h, take out, and vacuum dry to obtain modified aluminum nitride.

[0013] Furthermore, the preparation method of the polysilane coupling agent is as follows: A1. 1.8-2.0 parts by mass of 5-bromofurfural, 0.00037-0.00039 parts by mass of copper iodide, 0.0013-0.0015 parts by mass of bistriphenylphosphine palladium dichloride, and 43-44 parts by mass of triethylamine were mixed and stirred at 48-52°C under argon for 20-40 minutes. 1.08-1.1 parts by mass of trimethylsilylacetylene was added at a rate of 1 drop per second. The mixture was stirred at 50°C for 11-13 hours. After completion of the reaction, the mixture was concentrated under vacuum to remove unreacted triethylamine. The mixture was then separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain furfural disiloxane. The preparation mechanism of this step is that 5-bromofurfural and trimethylsilyl acetylene undergo Sonogashira coupling reaction to produce furfural disiloxane. The specific mechanism is as follows: ; A2. Furfural disiloxane, hydroxypolyethylene glycol triethoxysilane, and concentrated sulfuric acid are sequentially mixed, heated to reflux temperature, and water is added dropwise over 2.5-3.5 hours. After reflux for 6 hours, the mixture is subjected to atmospheric distillation at 110°C for 3 hours, cooled to room temperature, and dried to obtain a polysilane coupling agent. The molar ratio of furfural disiloxane to hydroxypolyethylene glycol triethoxysilane is 1-1.05:1, and the mass ratio of furfural disiloxane to concentrated sulfuric acid to water is 180.9:2-4:36.93-39.63.

[0014] Furthermore, the preparation method of the dispersant is as follows: B1. Coconut oil was added to a three-necked flask at room temperature. 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone were slowly added while stirring at 100 r / min. The mass ratio of coconut oil to 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone was 1:0.40-0.60:0.598-0.888. Solid potassium hydroxide was used as a catalyst in an amount less than 1% of the total mass of coconut oil and 3-Dimethylaminopropylamine. Nitrogen was introduced for 15 minutes. When the nitrogen pressure reached 0.2 MPa, the introduction was stopped. The reaction speed was increased to 300 r / min and the mixture was heated to 130-160°C for 5-8 hours. After the reaction was complete, the mixture was maintained at the same temperature and distilled under reduced pressure for 30 minutes. The mixture was then stopped and cooled to below 40°C. 3-Dimethylaminopropylamine was then removed by distillation under reduced pressure to obtain the intermediate tertiary amine. B2. Add 8-12 times the amount of deionized water to the intermediate tertiary amine while stirring at 100 r / min. Maintain the stirring speed at 58-62°C, add 1 / 4 of the mass fraction of chloroacetic acid aqueous solution, and simultaneously add 50% sodium hydroxide solution to adjust the pH to 9-11. At 60°C, add the remaining 3 / 4 of the mass fraction of 40% chloroacetic acid aqueous solution, and simultaneously add 50% mass fraction sodium hydroxide solution to adjust the pH to 9-11. Increase the stirring speed to 300 r / min and raise the temperature to 80-120°C. During this period, if the pH is lower than 9, add 50% mass fraction sodium hydroxide solution to adjust it. Maintain the reaction for 55-65 minutes. Subsequently, a 50% by mass sodium hydroxide solution was added to adjust the pH to between 9 and 11, and the reaction was continued for 110 to 130 minutes. A 50% by mass sodium hydroxide solution was added to control the pH of the reaction system to between 11.5 and 12.5, and the reaction was continued for 2.5 to 3.5 hours. Subsequently, the mixture was cooled to 70° C., benzoic acid was added, and the reaction was continued for 55 to 65 minutes. Subsequently, 37% by mass concentrated hydrochloric acid was added until the pH was 7, and the reaction was continued for 55 to 65 minutes to obtain a dispersant; wherein, the molar ratio of the intermediate tertiary amine to chloroacetic acid was 1:0.2 to 0.3; and the mass of benzoic acid was 0.011 to 0.013 times the mass of the intermediate tertiary amine.

[0015] Furthermore, the blending ratio of the mint fiber, modal fiber and mosquito-proof flax fiber is 20:60:20, and the linear density of the blended yarn is 11.8 tex.

[0016] By adopting the above technical solution, the present invention has the following beneficial effects: (1) The present invention prepares an environmentally friendly antibacterial plant-based fabric, which is woven by blending mint fiber, modal fiber and mosquito-proof flax fiber. Among them, mint fiber is a regenerated cellulose fiber with excellent moisture absorption and air permeability. The fabric made of it can bring a refreshing feeling when worn, and has good antibacterial and wearing properties. Modal fiber is also a regenerated cellulose fiber, which can be naturally degraded, is environmentally friendly, and has excellent skin-friendly comfort, high breaking strength, good spinnability and fine fiber fineness. After blending it and preparing fabric, the wearing properties and mechanical properties of the finished product can be significantly improved. In addition, the present invention also introduces flax fiber with mosquito-proof function to blend into yarn, so that the fabric has excellent mosquito-proof ability. The mint fiber, modal fiber and mosquito-proof flax fiber are blended and woven, and the environmentally friendly antibacterial plant-based fabric finally obtained has excellent performance in coolness, antibacterial, mosquito-proof and mechanical properties.

[0017] (2) The raw material components of the mosquito-proof flax fiber of the present invention include mugwort extract, modified aluminum nitride, dispersant, and flax fiber; mugwort is a plant of the Asteraceae family and the genus Artemisia, and contains a variety of organic compounds beneficial to the human body, the main components of which are tea polyphenols, caffeine, lipopolysaccharide, etc., which have antibacterial, deodorizing, mosquito-repellent, and health-care effects. The present invention introduces mugwort extract into the mosquito-proof flax fiber, which can give the mosquito-proof flax fiber better antibacterial and mosquito-repellent properties; aluminum nitride is a ceramic material with excellent performance, and its theoretical thermal conductivity is as high as 320W / (m·K), and it has the advantages of small thermal expansion coefficient, good chemical stability and environmental protection and non-toxicity. Introducing aluminum nitride into the mosquito-proof flax fiber can form a heat-conducting network in the mosquito-proof flax fiber, thereby making the mosquito-proof flax fiber have excellent performance in cooling. However, aluminum nitride has poor dispersibility and is very easy to agglomerate in the fiber, so aluminum nitride is modified to improve its dispersibility in the fiber, thereby ensuring or even improving the mechanical properties of the mosquito-proof flax fiber raw material.

[0018] (3) The present invention uses a silane coupling agent obtained by polymerization of furfural disiloxane and hydroxypolyethylene glycol triethoxysilane to modify aluminum nitride, which can effectively improve the dispersibility of aluminum nitride in the fiber, thereby ensuring or even improving the mechanical properties of the mosquito-proof flax fiber raw material.

[0019] (4) The present invention introduces a dispersant, which is obtained by a mixed reaction of coconut oil, 3-dimethylaminopropylamine, 2-hydroxy-4-aminoacetophenone, and aluminum acetic acid. Cationic quaternary ammonium salts and anionic carboxylates are formed in the dispersant, which act as electron donors and acceptors, respectively, to interact with hydrogen atoms in cellulose and oxygen atoms in hydroxyl groups, thereby breaking hydrogen bonds within cellulose and between cellulose molecules, causing the molecular chains to be destroyed, thereby achieving the decomposition of cellulose and dissolving it, and further enabling the wormwood extract, modified aluminum nitride, and flax fiber to be better and more evenly compounded together; The preparation mechanism of dispersants is as follows:

[0020] ; R1, R2, R3 represent C7~C 17 Alkyl carbon chain.

[0021] (5) The mosquito-proof flax fiber of the present invention is prepared by blending wormwood extract, modified aluminum nitride, dispersant and flax fiber and then putting them into a coagulation bath of a 25% sodium hydroxide aqueous solution and ethanol mixture for coagulation. The 2-hydroxyacetophenone on the modified aluminum nitride reacts with the furfural in the dispersant to undergo a Claisen-Schmidt reaction. After the formed molecular structure absorbs energy, the ground state molecule transitions to the first excited singlet state, and then crosses a smaller energy barrier to reach the S1 / S0 conical intersection point to relax the energy and reach the ground state. During the process, the dihedral angle of the carbon-carbon double bond rotates, and the molecular configuration undergoes cis-trans isomerization, thereby achieving the effect of ultraviolet absorption and giving the mosquito-proof flax fiber good sun protection performance.

[0022] The reaction mechanism of modified aluminum nitride and dispersant is as follows: . DETAILED DESCRIPTION

[0023] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0024] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0025] The following examples are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0026] Modal fiber: linear density 1.01dtex, elongation at break 12.37%, breaking strength 12.37cN*dtex -1 ; Mint fiber: linear density 1.39 dtex, elongation at break 19.14%, breaking strength 2.51 cN*dtex -1 ; The flax fiber is the recycled degummed flax fiber produced by Hangzhou Shanglu Silk Co., Ltd. Aluminum nitride is aluminum nitride with a particle size of 2 μm; Mugwort extract: Take the whole wormwood stem, wash and remove dust from it, cut the dust-removed wormwood stem into small sections with a length of about 2.5 cm, mix the wormwood sections with water, control the liquid ratio at 1:9, and cook at a temperature of 105°C for 40 minutes to obtain a cooking liquid, filter the cooking liquid, and use a filter material with a filter mesh of less than 10 μm to obtain the wormwood extract.

[0027] (Example 1) A method for preparing an environmentally friendly antibacterial plant-based fabric comprises the following steps: blending mint fiber, modal fiber, and mosquito-proof flax fiber in a blending ratio of 20:60:20 to obtain 11.8 tex yarn, and then weaving the yarn to obtain 160 g / m 2 Environmentally friendly antibacterial plant-based fabric.

[0028] The preparation method of the mosquito-proof flax fiber is as follows: (1) 4 parts by mass of dispersant were placed in a reaction vessel and stirred at 78°C for 55 minutes, followed by adding 0.25 parts by mass of flax fiber, and continuing to stir at 78°C until the flax fiber was dissolved. Then, 15 parts by mass of dimethyl sulfoxide were added, and stirring was continued at 78°C for 2.5 hours. Then, 0.12 parts by mass of modified aluminum nitride were added, and stirring was continued at 78°C for 25 minutes. Then, 0.007 parts by mass of wormwood extract was added, and mixing was continued at 25°C for 25 minutes to obtain a spinning solution. (2) The spinning solution obtained in step (1) was placed in a drying oven at 38°C for 11.5 hours for degassing; (3) The treated product in step (2) was loaded into a syringe and spun using a spinning machine. The spinning solution was squeezed into a coagulation bath of a mixture of 25% sodium hydroxide aqueous solution and ethanol in a volume ratio of 1:9 at a speed of 25 mm / h. The coagulation time was 6 h. The product was then washed twice with deionized water and dried in a drying oven at 60°C for 6 h to obtain 1.38 dtex mosquito-proof flax fiber.

[0029] The preparation method of the modified aluminum nitride is as follows: Pour the nano-aluminum nitride powder into a three-necked flask, use anhydrous ethanol 100 times the mass of the nano-aluminum nitride powder as the reaction solvent, heat in a water bath and add a polysilane coupling agent 0.04 times the mass of the nano-aluminum nitride powder under high-speed stirring, control the temperature to be constant at 54°C and react for 2.5 hours, then take it out, vacuum dry it in a vacuum drying oven at 48°C for 9.5 hours, grind it out and sieve it, then use acetone as the solvent for Soxhlet extraction for 24 hours, take it out and vacuum dry it to obtain modified aluminum nitride.

[0030] The preparation method of the polysilane coupling agent is as follows: A1. 1.8 parts by mass of 5-bromofurfural, 0.00037 parts by mass of copper iodide, 0.0013 parts by mass of bistriphenylphosphine palladium dichloride, and 43 parts by mass of triethylamine were mixed and stirred at 48°C under argon for 20 minutes. 1.08 parts by mass of trimethylsilylacetylene was added at a rate of 1 drop per second. The mixture was stirred at 50°C for 11 hours. After completion of the reaction, the mixture was concentrated under vacuum to remove unreacted triethylamine. The mixture was then separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain furfural disiloxane. A2. Furfural disiloxane, hydroxypolyethylene glycol triethoxysilane, and concentrated sulfuric acid were sequentially mixed, heated to reflux temperature, and water was added dropwise over 2.5 hours. After reflux for 6 hours, the mixture was distilled at atmospheric pressure at 110°C for 3 hours, cooled to room temperature, and dried to obtain a polysilane coupling agent. The molar ratio of furfural disiloxane to hydroxypolyethylene glycol triethoxysilane was 1:1, and the mass ratio of furfural disiloxane to concentrated sulfuric acid to water was 180.9:2:36.93.

[0031] The preparation method of the dispersant is as follows: B1. Coconut oil was added to a three-necked flask at room temperature. 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone were slowly added while stirring at 100 r / min. The mass ratio of coconut oil to 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone was 1:0.40:0.598. Solid potassium hydroxide was used as a catalyst in an amount less than 1% of the total mass of coconut oil and 3-Dimethylaminopropylamine. Nitrogen was introduced for 15 minutes. When the nitrogen pressure reached 0.2 MPa, the introduction was stopped. The reaction speed was increased to 300 r / min and the mixture was heated to 130°C for 5 hours. After the reaction was complete, the mixture was maintained at the same temperature and distilled under reduced pressure for 30 minutes. The mixture was then cooled to below 40°C and distilled under reduced pressure to remove 3-Dimethylaminopropylamine to obtain the intermediate tertiary amine. B2. Add 8 times the amount of deionized water as the intermediate tertiary amine under stirring at 100 r / min. At 58°C, maintain the stirring speed unchanged, add 1 / 4 of the mass fraction of chloroacetic acid aqueous solution, and simultaneously add 50% sodium hydroxide solution to adjust the pH to 9. At 60°C, add the remaining 3 / 4 of the mass fraction of 40% chloroacetic acid aqueous solution, and simultaneously add 50% mass fraction sodium hydroxide solution to adjust the pH to 9. Increase the stirring speed to 300 r / min and raise the temperature to 80°C. During this period, if the pH is lower than 9, add 50% mass fraction sodium hydroxide solution to adjust it. Maintain the reaction temperature. The mixture was stirred for 55 minutes, and then 50% by mass sodium hydroxide solution was added to adjust the pH to 9. The reaction was continued for 110 minutes, and 50% by mass sodium hydroxide solution was added to control the pH of the reaction system to be between 11.5. The reaction was continued for 2.5 hours, and then cooled to 70°C, benzoic acid was added, and the reaction was continued for 55 minutes. Then, 37% by mass concentrated hydrochloric acid was added to pH 7, and the reaction was continued for 55 minutes to obtain a dispersant; wherein, the molar ratio of the intermediate tertiary amine to chloroacetic acid was 1:0.2; the mass of benzoic acid was 0.011 times the mass of the intermediate tertiary amine.

[0032] (Example 2) A method for preparing an environmentally friendly antibacterial plant-based fabric comprises the following steps: blending mint fiber, modal fiber, and mosquito-proof flax fiber in a blending ratio of 20:60:20 to obtain 11.8 tex yarn, and then weaving the yarn to obtain 160 g / m 2 Environmentally friendly antibacterial plant-based fabric.

[0033] The preparation method of the mosquito-proof flax fiber is as follows: (1) 5 parts by mass of dispersant were placed in a reaction vessel and stirred at 80°C for 60 minutes, followed by adding 0.25 parts by mass of flax fiber, and continuing to stir at 80°C until the flax fiber was dissolved. Then, 15.5 parts by mass of dimethyl sulfoxide were added, and stirring was continued at 80°C for 3 hours. Then, 0.125 parts by mass of modified aluminum nitride were added, and stirring was continued at 80°C for 30 minutes. Then, 0.008 parts by mass of wormwood extract was added, and mixing was continued at 25°C for 30 minutes to obtain a spinning solution. (2) The spinning solution obtained in step (1) was placed in a drying oven at 40°C for 12 hours for degassing; (3) The treated product in step (2) was loaded into a syringe and spun using a spinning machine. The spinning solution was squeezed into a coagulation bath of a mixture of 25% sodium hydroxide aqueous solution and ethanol in a volume ratio of 1:10 at a speed of 30 mm / h. The coagulation time was 6 h. The product was then washed with deionized water three times and dried in a drying oven at 60°C for 6 h to obtain 1.38 dtex mosquito-proof flax fiber.

[0034] The preparation method of the modified aluminum nitride is as follows: Pour the nano-aluminum nitride powder into a three-necked flask, use anhydrous ethanol 100 times the mass of the nano-aluminum nitride powder as the reaction solvent, heat in a water bath and add a polysilane coupling agent 0.05 times the mass of the nano-aluminum nitride powder under high-speed stirring, control the temperature to be constant at 55°C and react for 3 hours, then take it out, vacuum dry it in a vacuum drying oven at 50°C for 10 hours, grind it out and sieve it, then use acetone as the solvent for Soxhlet extraction for 24 hours, take it out and vacuum dry it to obtain modified aluminum nitride.

[0035] The preparation method of the polysilane coupling agent is as follows: A1. 1.9 parts by mass of 5-bromofurfural, 0.00038 parts by mass of copper iodide, 0.0014 parts by mass of bistriphenylphosphine palladium dichloride, and 43.5 parts by mass of triethylamine were mixed and stirred at 50°C under argon for 30 minutes. 1.09 parts by mass of trimethylsilylacetylene was added at a rate of 1 drop per second. The mixture was stirred at 50°C for 12 hours. After completion of the reaction, the mixture was concentrated under vacuum to remove unreacted triethylamine. The mixture was then separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain furfural disiloxane. A2. Furfural disiloxane, hydroxypolyethylene glycol triethoxysilane, and concentrated sulfuric acid were sequentially mixed, heated to reflux temperature, and water was added dropwise over 3 hours. After reflux for 6 hours, the mixture was distilled at atmospheric pressure at 110°C for 3 hours, cooled to room temperature, and dried to obtain a polysilane coupling agent. The molar ratio of furfural disiloxane to hydroxypolyethylene glycol triethoxysilane was 1.025:1, and the mass ratio of furfural disiloxane to concentrated sulfuric acid to water was 180.9:3:38.

[0036] The preparation method of the dispersant is as follows: B1. Coconut oil was added to a three-necked flask at room temperature. 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone were slowly added while stirring at 100 r / min. The mass ratio of coconut oil to 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone was 1:0.5:0.743. Solid potassium hydroxide was used as a catalyst in an amount less than 1% of the total mass of coconut oil and 3-Dimethylaminopropylamine. Nitrogen was introduced for 15 minutes. When the nitrogen pressure reached 0.2 MPa, the introduction was stopped. The reaction speed was increased to 300 r / min and the mixture was heated to 145°C for 6.5 hours. After the reaction was complete, the mixture was maintained at the same temperature and distilled under reduced pressure for 30 minutes. The mixture was then cooled to below 40°C and distilled under reduced pressure to remove 3-Dimethylaminopropylamine to obtain the intermediate tertiary amine. B2. Add 10 times the amount of deionized water as the intermediate tertiary amine under stirring at 100 r / min. At 60°C, maintain the stirring speed unchanged, add 1 / 4 of the mass fraction of chloroacetic acid aqueous solution, and simultaneously add 50% sodium hydroxide solution to adjust the pH to 10. At 60°C, add the remaining 3 / 4 of the mass fraction of 40% chloroacetic acid aqueous solution, and simultaneously add 50% mass fraction sodium hydroxide solution to adjust the pH to 10. Increase the stirring speed to 300 r / min and raise the temperature to 100°C. During this period, if the pH is lower than 9, add 50% mass fraction sodium hydroxide solution to adjust it. The reaction was maintained for 60 minutes, and then a 50% by mass sodium hydroxide solution was added to adjust the pH to 10. The reaction was continued for 120 minutes, and a 50% by mass sodium hydroxide solution was added to control the pH of the reaction system to 12. The reaction was continued for 3 hours, and then cooled to 70°C, benzoic acid was added, and the reaction was continued for 60 minutes. Then, 37% by mass concentrated hydrochloric acid was added to a pH of 7, and the reaction was continued for 60 minutes to obtain a dispersant; wherein the molar ratio of the intermediate tertiary amine to chloroacetic acid was 1:0.25; the mass of benzoic acid was 0.012 times the mass of the intermediate tertiary amine.

[0037] (Example 3) A method for preparing an environmentally friendly antibacterial plant-based fabric comprises the following steps: blending mint fiber, modal fiber, and mosquito-proof flax fiber in a blending ratio of 20:60:20 to obtain 11.8 tex yarn, and then weaving the yarn to obtain 160 g / m 2 Environmentally friendly antibacterial plant-based fabric.

[0038] The preparation method of the mosquito-proof flax fiber is as follows: (1) 6 parts by mass of dispersant were placed in a reaction vessel and stirred at 82°C for 65 minutes, followed by adding 0.25 parts by mass of flax fiber, and continuing to stir at 82°C until the flax fiber was dissolved. Then, 16 parts by mass of dimethyl sulfoxide were added, and stirring was continued at 82°C for 3.5 hours. Then, 0.13 parts by mass of modified aluminum nitride were added, and stirring was continued at 82°C for 35 minutes. Then, 0.009 parts by mass of wormwood extract was added, and mixing was continued at 25°C for 35 minutes to obtain a spinning solution. (2) The spinning solution obtained in step (1) was placed in a drying oven at 42°C for 12.5 hours for degassing; (3) The treated fiber in step (2) was loaded into a syringe and spun using a spinning machine. The spinning solution was squeezed into a coagulation bath of a mixture of 25% sodium hydroxide aqueous solution and ethanol in a volume ratio of 1:11 at a speed of 35 mm / h. The coagulation time was 6 h. The fiber was then washed with deionized water 4 times and dried in a drying oven at 60°C for 6 h to obtain 1.38 dtex mosquito-proof flax fiber.

[0039] The preparation method of the modified aluminum nitride is as follows: Pour the nano-aluminum nitride powder into a three-necked flask, use anhydrous ethanol 100 times the mass of the nano-aluminum nitride powder as the reaction solvent, heat in a water bath and add a polysilane coupling agent 0.06 times the mass of the nano-aluminum nitride powder under high-speed stirring, control the temperature to be constant at 56°C and react at this temperature for 3.5 hours, then take it out, vacuum dry it in a vacuum drying oven at 52°C for 10.5 hours, grind it out and sieve it, then use acetone as the solvent for Soxhlet extraction for 24 hours, take it out, and vacuum dry it to obtain modified aluminum nitride.

[0040] The preparation method of the polysilane coupling agent is as follows: A1. 2.0 parts by mass of 5-bromofurfural, 0.00039 parts by mass of copper iodide, 0.0015 parts by mass of bistriphenylphosphine palladium dichloride, and 44 parts by mass of triethylamine were mixed and stirred at 52°C under argon for 40 minutes. 1.1 parts by mass of trimethylsilylacetylene was added at a rate of 1 drop per second. The mixture was stirred at 50°C for 13 hours. After completion of the reaction, the mixture was concentrated under vacuum to remove unreacted triethylamine. The mixture was then separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain furfural disiloxane. A2. Furfural disiloxane, hydroxypolyethylene glycol triethoxysilane, and concentrated sulfuric acid were sequentially mixed, heated to reflux temperature, and water was added dropwise over 3.5 hours. After reflux for 6 hours, the mixture was distilled at atmospheric pressure at 110°C for 3 hours, cooled to room temperature, and dried to obtain a polysilane coupling agent. The molar ratio of furfural disiloxane to hydroxypolyethylene glycol triethoxysilane was 1.05:1, and the mass ratio of furfural disiloxane to concentrated sulfuric acid to water was 180.9:4:39.63.

[0041] The preparation method of the dispersant is as follows: B1. Coconut oil was added to a three-necked flask at room temperature. 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone were slowly added while stirring at 100 r / min. The mass ratio of coconut oil to 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone was 1:0.60:0.888. Solid potassium hydroxide was used as a catalyst in an amount less than 1% of the total mass of coconut oil and 3-Dimethylaminopropylamine. Nitrogen was introduced for 15 minutes. When the nitrogen pressure reached 0.2 MPa, the introduction was stopped. The reaction speed was increased to 300 r / min and the mixture was heated to 160°C for 8 hours. After the reaction was complete, the mixture was maintained at the same temperature and distilled under reduced pressure for 30 minutes. The mixture was then cooled to below 40°C and distilled under reduced pressure to remove 3-Dimethylaminopropylamine to obtain the intermediate tertiary amine. B2. Add 12 times the amount of deionized water to the intermediate tertiary amine under stirring at 100 r / min. At 62°C, maintain the stirring speed unchanged, add 1 / 4 of the mass fraction of chloroacetic acid aqueous solution, and simultaneously add 50% sodium hydroxide solution to adjust the pH to 11. At 60°C, add the remaining 3 / 4 of the mass fraction of 40% chloroacetic acid aqueous solution, and simultaneously add 50% mass fraction of sodium hydroxide solution to adjust the pH to 11. Increase the stirring speed to 300 r / min and raise the temperature to 120°C. During this period, if the pH is lower than 9, add 50% mass fraction of sodium hydroxide solution to adjust it and maintain The mixture was reacted for 65 minutes, and then a 50% by mass sodium hydroxide solution was added to adjust the pH to 11. The reaction was continued for 130 minutes, and a 50% by mass sodium hydroxide solution was added to control the pH of the reaction system to be between 12.5. The reaction was continued for 3.5 hours, and then the mixture was cooled to 70°C, benzoic acid was added, and the reaction was continued for 65 minutes. Subsequently, 37% by mass concentrated hydrochloric acid was added to a pH of 7, and the reaction was continued for 65 minutes to obtain a dispersant. The molar ratio of the intermediate tertiary amine to chloroacetic acid was 1:0.3, and the mass of benzoic acid was 0.013 times the mass of the intermediate tertiary amine.

[0042] (Comparative Example 1) The difference between Comparative Example 1 and Example 2 is that 1-butyl-3-methylimidazolium chloride is used as the dispersant, and the remaining steps and components are the same as those in Example 2.

[0043] (Comparative Example 2) The difference between Comparative Example 2 and Example 2 is that the raw material components of the mosquito repellent flax fiber include wormwood extract, aluminum nitride, dispersant, and flax fiber, and the remaining steps and components are the same as those of Example 2.

[0044] (Comparative Example 3) The difference between Comparative Example 3 and Example 2 is that the modified aluminum nitride is obtained by modification with γ-aminopropyltriethoxysilane, and the remaining steps and components are the same as those in Example 2.

[0045] (Comparative Example 4) The difference between Comparative Example 4 and Example 2 is that the anti-mosquito flax fiber raw material components include wormwood extract, dispersant, and flax fiber, and the remaining steps and components are the same as Example 2.

[0046] (Effect example) Cooling coefficient: Refer to GB / T35263-2017 "Test and evaluation of instantaneous cooling properties of textiles" standard. Under the specified test environment conditions, the heat detection plate is brought into contact with the sample on the sample carrier. The temperature change of the heat detection plate over time is measured and the contact cooling coefficient is calculated. The sample size is 20cm×20cm, the mass of the hot plate is 90g, and the contact area is 9cm. 2 , the initial temperature of the hot plate is (35±0.5)℃.

[0047] Sun protection performance: Refer to GB / T 18830-2009 "Evaluation of the UV protection performance of textiles" to test the UPF ultraviolet protection factor; among them, the ultraviolet protection factor UPF is currently the most widely used indicator at home and abroad to evaluate the UV protection performance of fabrics. It represents the ability of fabrics to protect against ultraviolet rays. It is the ratio of the average amount of ultraviolet radiation on unprotected skin to the ultraviolet radiation energy after being blocked by the tested fabric. The method for judging the sun protection performance of fabrics is: UPF ≤ 14, poor; 15 ≤ UPF ≤ 24, relatively good; 25 ≤ UPF ≤ 39, good; UPF ≥ 40, very good.

[0048] Mechanical properties: According to GB / T14337-2008 "Test method for tensile properties of chemical staple fibers", the breaking strength of mosquito repellent flax fibers was measured using an LLY-06EDC electronic single fiber strength tester. The test parameters were: clamping distance 10 mm, tensile speed 5 mm / min, 50 tests, and the results were averaged.

[0049] Antibacterial rate: The antibacterial rate of Escherichia coli of environmentally friendly antibacterial plant-based fabrics is tested according to FZ / T73023-2006 "Antibacterial Knitwear".

[0050] Table 1 below shows the performance test results of environmentally friendly antibacterial plant-based fabrics and mosquito-proof flax fibers: Table 1

[0051] As can be seen from Table 1, the environmentally friendly antibacterial plant-based fabrics prepared in Examples 1 to 3 have good antibacterial and sun protection properties, can provide an instant cooling feeling, and their anti-mosquito and insect repellent flax fibers have good mechanical properties, and thus the prepared environmentally friendly antibacterial plant-based fabrics have good mechanical properties; the difference between Comparative Example 1 and Example 2 is that the dispersant uses 1-butyl-3-methylimidazolium chloride, and the prepared environmentally friendly antibacterial plant-based fabrics have weaker sun protection and cooling properties, and their anti-mosquito and insect repellent flax fibers have weaker mechanical properties.

[0052] The difference between Comparative Example 2 and Example 2 is that the raw material component of the mosquito-proof flax fiber uses aluminum nitride instead of modified aluminum nitride. The sun protection of the obtained environmentally friendly antibacterial plant-based fabric is weak, the aluminum nitride agglomeration cannot form a heat conduction network, and the cooling performance is weak. The agglomeration of aluminum nitride causes the mechanical properties of the mosquito-proof flax fiber to weaken.

[0053] The difference between Comparative Example 3 and Example 2 is that the modified aluminum nitride is modified by γ-aminopropyltriethoxysilane, and the obtained environmentally friendly antibacterial plant-based fabric has poor sun protection and weak cooling performance. This shows that the embodiment uses a silane coupling agent obtained by polymerization of furfural disiloxane and hydroxypolyethylene glycol triethoxysilane to modify aluminum nitride, which improves the interface state between aluminum nitride and other components of the mosquito repellent flax fiber, reduces thermal resistance, improves thermal conductivity, and thus improves cooling performance.

[0054] The difference between Comparative Example 4 and Example 2 is that modified aluminum nitride is not added to the anti-mosquito flax fiber raw material component, and the obtained environmentally friendly antibacterial plant-based fabric has poor sun protection and weak cooling performance, and the mechanical properties of its anti-mosquito flax fiber are poor, and thus the obtained environmentally friendly antibacterial plant-based fabric has poor mechanical properties.

[0055] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An environmentally friendly antibacterial plant-based fabric, characterized in that: The environmentally friendly antibacterial plant-based fabric is woven by blending mint fiber, modal fiber and mosquito-proof flax fiber; the raw material components of the mosquito-proof flax fiber include wormwood extract, modified aluminum nitride, dispersant and flax fiber.

2. The environmentally friendly antibacterial plant-based fabric according to claim 1, characterized in that: The modified aluminum nitride is obtained by coating the modified aluminum nitride with a polysiloxane coupling agent.

3. The environmentally friendly antibacterial plant-based fabric according to claim 2, characterized in that: The polysilane coupling agent is obtained by polymerization of furfural disiloxane and hydroxypolyethylene glycol triethoxysilane.

4. The environmentally friendly antibacterial plant-based fabric according to claim 1, characterized in that: The dispersant is obtained by mixing coconut oil, 3-dimethylaminopropylamine, 2-hydroxy-4-aminoacetophenone and aluminum acetic acid.

5. A method for preparing the environmentally friendly antibacterial plant-based fabric according to any one of claims 1 to 4, characterized in that: The method comprises the following preparation steps: blending and weaving mint fiber, modal fiber and mosquito-proof flax fiber to obtain an environmentally friendly and antibacterial plant-based fabric.

6. The method for preparing the environmentally friendly antibacterial plant-based fabric according to claim 5, characterized in that: The preparation method of the mosquito-proof flax fiber is as follows: (1) 4-6 parts by weight of dispersant were placed in a reaction vessel and stirred at 78-82°C for 55-65 minutes, followed by adding 0.25 parts by weight of flax fiber and continuing to stir at 78-82°C until the flax fiber was dissolved. Then, 15-16 parts by weight of dimethyl sulfoxide were added and continued to stir at 78-82°C for 2.5-3.5 hours. Then, 0.12-0.13 parts by weight of modified aluminum nitride were added and continued to stir at 78-82°C for 25-35 minutes. Then, 0.007-0.009 parts by weight of wormwood extract were added and mixed at 25°C for 25-35 minutes to obtain a spinning solution. (2) the spinning solution obtained in step (1) was placed in a drying oven at 38-42°C for 11.5-12.5 hours for degassing; (3) The treated product in step (2) is loaded into a syringe and spun using a spinning machine. The spinning solution is squeezed into a coagulation bath of a mixed solution of 25% sodium hydroxide aqueous solution and ethanol in a volume ratio of 1:9-11 at a speed of 25-35 mm / h. The coagulation time is 6 hours. The product is then washed with deionized water 2-4 times and dried in a drying oven at 60°C for 6 hours to obtain mosquito-proof flax fiber.

7. The method for preparing the environmentally friendly antibacterial plant-based fabric according to claim 6, characterized in that: The preparation method of the modified aluminum nitride is as follows: Pour the nano-aluminum nitride powder into a three-necked flask, use anhydrous ethanol 100 times the mass of the nano-aluminum nitride powder as the reaction solvent, heat in a water bath and add a polysilane coupling agent 0.04~0.06 times the mass of the nano-aluminum nitride powder under high-speed stirring, control the temperature to be constant at 54~56°C for constant temperature reaction for 2.5~3.5h, take out, vacuum dry in a vacuum drying oven at 48~52°C for 9.5~10.5h, grind and sieve after taking out, then use acetone as solvent for Soxhlet extraction for 24h, take out, and vacuum dry to obtain modified aluminum nitride.

8. The method for preparing the environmentally friendly antibacterial plant-based fabric according to claim 7, characterized in that: The preparation method of the polysilane coupling agent is as follows: A1. 1.8-2.0 parts by mass of 5-bromofurfural, 0.00037-0.00039 parts by mass of copper iodide, 0.0013-0.0015 parts by mass of bistriphenylphosphine palladium dichloride, and 43-44 parts by mass of triethylamine were mixed and stirred at 48-52°C under argon for 20-40 minutes. 1.08-1.1 parts by mass of trimethylsilylacetylene was added at a rate of 1 drop per second. The mixture was stirred at 50°C for 11-13 hours. After completion of the reaction, the mixture was concentrated under vacuum to remove unreacted triethylamine. The mixture was then separated and purified by silica gel column chromatography using petroleum ether / ethyl acetate as the eluent to obtain furfural disiloxane. A2. Furfural disiloxane, hydroxypolyethylene glycol triethoxysilane, and concentrated sulfuric acid are sequentially mixed, heated to reflux temperature, and water is added dropwise over 2.5-3.5 hours. After reflux for 6 hours, the mixture is subjected to atmospheric distillation at 110°C for 3 hours, cooled to room temperature, and dried to obtain a polysilane coupling agent. The molar ratio of furfural disiloxane to hydroxypolyethylene glycol triethoxysilane is 1-1.05:1, and the mass ratio of furfural disiloxane to concentrated sulfuric acid to water is 180.9:2-4:36.93-39.

63.

9. The method for preparing the environmentally friendly antibacterial plant-based fabric according to claim 6, characterized in that: The preparation method of the dispersant is as follows: B1. Coconut oil was added to a three-necked flask at room temperature. 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone were slowly added while stirring at 100 r / min. The mass ratio of coconut oil to 3-Dimethylaminopropylamine and 2-hydroxy-4-aminoacetophenone was 1:0.40-0.60:0.598-0.

888. Solid potassium hydroxide was used as a catalyst in an amount less than 1% of the total mass of coconut oil and 3-Dimethylaminopropylamine. Nitrogen was introduced for 15 minutes. When the nitrogen pressure reached 0.2 MPa, the introduction was stopped. The reaction speed was increased to 300 r / min and the mixture was heated to 130-160°C for 5-8 hours. After the reaction was complete, the mixture was maintained at the same temperature and distilled under reduced pressure for 30 minutes. The mixture was then stopped and cooled to below 40°C. 3-Dimethylaminopropylamine was then removed by distillation under reduced pressure to obtain the intermediate tertiary amine. B2. Add 8-12 times the amount of deionized water to the intermediate tertiary amine while stirring at 100 r / min. Maintain the stirring speed at 58-62°C, add 1 / 4 of the mass fraction of chloroacetic acid aqueous solution, and simultaneously add 50% sodium hydroxide solution to adjust the pH to 9-11. At 60°C, add the remaining 3 / 4 of the mass fraction of 40% chloroacetic acid aqueous solution, and simultaneously add 50% mass fraction sodium hydroxide solution to adjust the pH to 9-11. Increase the stirring speed to 300 r / min and raise the temperature to 80-120°C. During this period, if the pH is lower than 9, add 50% mass fraction sodium hydroxide solution to adjust it. Maintain the reaction for 55-65 minutes. Subsequently, a 50% by mass sodium hydroxide solution was added to adjust the pH to between 9 and 11, and the reaction was continued for 110 to 130 minutes. A 50% by mass sodium hydroxide solution was added to control the pH of the reaction system to between 11.5 and 12.5, and the reaction was continued for 2.5 to 3.5 hours. Subsequently, the mixture was cooled to 70° C., benzoic acid was added, and the reaction was continued for 55 to 65 minutes. Subsequently, 37% by mass concentrated hydrochloric acid was added until the pH was 7, and the reaction was continued for 55 to 65 minutes to obtain a dispersant; wherein, the molar ratio of the intermediate tertiary amine to chloroacetic acid was 1:0.2 to 0.3; and the mass of benzoic acid was 0.011 to 0.013 times the mass of the intermediate tertiary amine.

10. The method for preparing the environmentally friendly antibacterial plant-based fabric according to claim 6, characterized in that: The blending ratio of the mint fiber, modal fiber and mosquito-proof flax fiber is 20:60:20, and the linear density of the blended yarn is 11.8 tex.

Images