Waterproof aromatic dyeing yarn and preparation method thereof

Abstract

The application discloses a waterproof aromatic dyeing yarn and a preparation method thereof, and relates to the technical field of yarns.The modified cellulose is obtained by using chitosan, 2,4-hydroxybenzaldehyde, 4-bromo-3-mercaptobenzoic acid and 10-alkenylundecyloxytrimethylsilane to modify cellulose, benzophenone, Schiff base and chitosan are introduced into the cellulose molecular chain, the functions of bacteriostasis and sterilization and ultraviolet absorption can be realized, long-chain silane groups are also introduced to improve the waterproof effect of the yarn;then aromatic microcapsules are formed by emulsifying plant aromatic essential oil, the aromatic smell can be effectively and continuously diffused, the modified fiber can be fully mixed with the aromatic microcapsules, the hydrophobic property of the modified fiber makes the perfume not easy to be washed away, the smell is more persistent, then the yarn is immersed in active fuel, sodium sulfate is used for promoting dyeing, and the dyeing yarn is obtained.The yarn prepared by the application has the effects of antibiosis, waterproofness and ultraviolet resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of yarn, in particular to a waterproof aromatic dyed yarn and a preparation method thereof. BACKGROUND

[0002] With the improvement of living standards, the requirements for garment fabrics are getting higher and higher, especially the functional requirements for fabrics. Waterproof functional fabrics are more and more popular with consumers. Generally, waterproof finishing is carried out on cotton fibers. The conventional waterproof finishing agent is generally aluminum sulfate, a fatty acid chromium complex, and an ammonium compound of a long-chain aliphatic hydrocarbon. A coating layer is formed on the fabric by adopting the method of dip padding and then baking. This method is complex, long in process, high in energy consumption, and only has semi-durable or non-durable characteristics. The finished fabric or yarn has a hard hand feeling. Similarly, natural fibers such as cotton fibers can be decomposed as a growth material for microorganisms and become a breeding ground for microorganisms when used. In addition, the yarn is thin, has a large specific surface area, and can absorb more ultraviolet rays under sunlight, and has poor ultraviolet resistance. SUMMARY

[0003] The present application aims to provide a waterproof aromatic dyed yarn and a preparation method thereof to solve the problems in the prior art.

[0004] In order to solve the above technical problems, the present application provides the following technical scheme: a waterproof aromatic dyed yarn is prepared by mixing and spinning aromatic microcapsules and modified cellulose, and then performing dyeing treatment.

[0005] Further, the modified cellulose is prepared from chitosan, 2,4-hydroxybenzaldehyde, 4-bromo-3-mercaptobenzoic acid, 10-alkenylundecyloxytrimethylsilane, and brominated cellulose.

[0006] Further, a preparation method of a waterproof aromatic dyed yarn includes the following preparation steps:

[0007] (1) Disperse chitosan in methanol with a mass of 40-60 times that of chitosan, swell for 1 h, then heat to 40-50 DEG C, add 2,4-hydroxybenzaldehyde alcohol solution with a mass of 9.0-15.4 times that of chitosan, react for 10-12 h, then filter, wash with methanol and deionized water for 4 times in sequence, add anhydrous ethanol with a mass of 14-22 times that of chitosan, extract at 75-82 DEG C for 12 h, then filter, dry at 50 DEG C under a vacuum degree of -0.08 MPa for 10 h to obtain a Schiff base compound;

[0008] (2) mixing the Schiff base compound, 1, 2-dichloroethane, 4-bromo-3-mercaptobenzoic acid according to the mass ratio of 1:6:0.9-1:12:1.2, placing in an ice bath under argon protection, stirring at 60-80 rpm for 10 min, adding 4-5 times the mass of the Schiff base compound of Eaton reagent, continuing to stir for 30 min, removing the ice bath, continuing to stir at room temperature for 30-50 min, placing in an oil bath, warming to 50-60℃, reacting for 12 h, cooling to room temperature, extracting with water 3 times, taking the organic layer, extracting with saturated brine 1 time, drying with anhydrous sodium sulfate for 1 h, filtering, concentrating under vacuum at-0.06 MPa and 60℃ for 3-4 h, drying at 80℃ for 24 h to obtain the benzophenone compound;

[0009] (3) mixing the benzophenone compound, 10-alkenylundecyloxymethylsilane, dichloromethane, triethylamine according to the mass ratio of 1:0.5:7:0.08-1:0.7:11:0.1, reacting at room temperature for 6-10 h, warming to 50℃, reacting for 4-7 h to obtain the organosilicon compound;

[0010] (4) mixing the pretreated cellulose, anhydrous tetrahydrofuran, triethylamine, 4-dimethylaminopyridine, 2-bromoisobutyryl bromide solution according to the mass ratio of 1:89:1.95:0.5:31.7, sealing and stirring at 60-80 rpm for 24 h under a nitrogen atmosphere at 25℃, centrifuging with anhydrous ethanol, anhydrous tetrahydrofuran and acetone at 8000 rpm for 8-15 min respectively to obtain the brominated cellulose;

[0011] (5) mixing the brominated cellulose, N,N-dimethylformamide, hexamethylene diisocyanate according to the mass ratio of 1:5:0.5, stirring at 60℃ and 80 rpm for 7-8 h, then adding 5-8 times the mass of the brominated cellulose of N,N-dimethylformamide and 0.5-0.8 times the mass of the brominated cellulose of the organosilicon compound, continuing to stir at the same temperature for 12-14 h, washing with deionized water 6 times, drying at 90℃ under a vacuum of-0.08 MPa for 24 h to obtain the modified cellulose;

[0012] (6) mixing the modified cellulose, aromatic microcapsules, N,N-dimethylacetamide according to the mass ratio of 1:0.2:5-1:0.5:5, stirring at 45-55℃ and 100 rpm for 30-60 min, electrospinning, then twisting at 20-40 twists / 10 cm to obtain the 30-35 dtex yarn; placing the yarn in a dyeing solution according to a bath ratio of 1:20, the mass ratio of reactive dyes and deionized water in the dyeing solution being 1:24-1:49, immersing for 10-30 min, taking out, placing in a salt bath according to a bath ratio of 1:20, immersing at 55-65℃ for 3-5 min, taking out, steam fixing at 100-105℃ for 8-10 min, washing with cold water 2-3 times, drying at 60℃ for 12 h to obtain the waterproof aromatic dyed yarn.

[0013] Further, the 2,4-hydroxybenzaldehyde alcohol solution in step (1) is a mixture of 2,4-hydroxybenzaldehyde and anhydrous ethanol with a mass ratio of 1:6.

[0014] Further, the preparation method of the pretreated fiber in step (4) is as follows: cotton cellulose and a 64% sulfuric acid solution are mixed with a mass ratio of 1:15.5, and then stirred at 50 DEG C and 100 rpm for 1-2 h; 10 times the volume of deionized water is added, and then centrifuged at 8000 rpm for 20-30 min; the pretreated cellulose is obtained by placing the centrifuged product in a dialysis bag with a molecular weight of 8000-14000 and dialyzing with deionized water for 7 d.

[0015] Further, the 2-bromoisobutyryl bromide solution in step (4) is a mixture of 2-bromoisobutyryl bromide and anhydrous tetrahydrofuran with a mass ratio of 1:5.34.

[0016] Further, the preparation method of the aromatic microcapsule in step (6) is as follows: a gelatin aqueous solution with a mass fraction of 0.5-2.5% and an acacia aqueous solution with a mass fraction of 0.5-2.5% are mixed with a volume ratio of 1:1 to obtain a wall material solution; the wall material solution is added to jasmine absolute oil with a core-wall ratio of 1:1-1:3; the mixture is stirred at 10000 rpm for 3-5 min under a water bath at 50 DEG C; the water bath temperature is lowered to 40 DEG C; the mixture is stirred at 200-800 rpm for 30 min; acetic acid is added to the solution until the pH is 3.1-4.3; the solution is reacted for 30-40 min; the temperature is lowered to 10 DEG C; sodium bicarbonate is added to the solution until the pH is 6; transglutaminase is added to the solution with an amount of 0.06 times the mass of the wall material solution; the solution is continuously reacted for 4-8 h; the solution is filtered and washed with deionized water by centrifugation for 3 times; and the aromatic microcapsule is obtained by drying the solution at 60 DEG C for 24 h.

[0017] Further, the spinning conditions in step (6) are as follows: the temperature is 30 DEG C; the inner diameter of the needle tip is 0.1 mm; the collection distance is 15-20 cm; the electric field strength is 1.0-1.4 kV / cm; and the extrusion rate is 0.02-0.06 mL / min; and the salt and alkali bath is composed of 20-30 g / L of sodium sulfate and 40-50 g / L of sodium carbonate.

[0018] Compared with the prior art, the present application has the following beneficial effects:

[0019] The application utilizes plant aromatic essential oil to form aromatic microcapsules by emulsification, can effectively and continuously disperse aromatic odor, has the effect of relaxing and making people feel happy, meanwhile, by utilizing the microcapsule structure, the essential oil can be effectively protected and stored, can be fully mixed with modified fibers, the loss of spices is small, the cost is saved, is suitable for large-scale production, meanwhile, the hydrophobicity of the modified fibers makes the spices not easy to be washed off, the fragrance is more lasting, then is immersed in active fuel, sodium sulfate is used for promoting dyeing, and dyed yarn is obtained, so as to realize the effects of antibacterial, waterproof and ultraviolet resistance.

[0020] The application utilizes chitosan as raw material, can be adsorbed on the cell surface to form a high molecular film, prevent the transportation of nutrients into the cell, thereby play the role of bacteriostasis and sterilization, utilize the amino group and the aldehyde group of 2,4-hydroxybenzaldehyde to form Schiff base, introduce the Schiff base structure on the molecular chain of chitosan, improve the antibacterial activity of chitosan, thereby improve the antibacterial property of the yarn, then, the aryl group of 2,4-hydroxybenzaldehyde reacts with the carboxyl group of 4-bromo-3-mercaptobenzoic acid to form benzophenone structure, can absorb ultraviolet light, improve the ultraviolet resistance effect of the yarn, then, the mercapto group of 4-bromo-3-mercaptobenzoic acid reacts with the double bond of 10-alkenylundecyloxytrimethylsilane to introduce long-chain silane groups, improve the waterproof effect of the yarn, and then graft the hydroxyl group on the brominated cellulose to obtain modified cellulose. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be clearly and completely described below in combination with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0022] In order to more clearly illustrate the method provided by the application, the following embodiments are used for detailed description, and the test methods of various indexes of the waterproof aromatic dyed yarn prepared in the following embodiments are as follows:

[0023] Waterproof: the same quality of the examples and the comparative examples is hung, water is sprayed from above the yarn by using AATTCC spray tester for 5 min, and then the time for the yarn to stop dripping water is observed.

[0024] Antibacterial: the same quality of the examples and the comparative examples is taken, and the escherichia coli inhibition rate is tested according to GB / T20944.3.

[0025] Anti-ultraviolet: the same number and quality of the examples and the comparative examples are woven into fabrics, and the ultraviolet protection coefficient is tested according to GB / T18830.

[0026] Example 1

[0027] (1) The chitosan is dispersed in 40 times the mass of chitosan of methanol, swells for 1 h, and then is heated to 40℃. 9 times the mass of chitosan of 2,4-hydroxybenzaldehyde alcohol solution is added. The mass ratio of 2,4-hydroxybenzaldehyde to anhydrous ethanol in the 2,4-hydroxybenzaldehyde alcohol solution is 1:6. After 10 h of reaction, suction filtration is performed, and then the product is washed with methanol and deionized water four times in sequence. 14 times the mass of chitosan of anhydrous ethanol is added. After 12 h of extraction at 75℃, suction filtration is performed, and then the product is dried at 50℃ under a vacuum of-0.08 MPa for 10 h to obtain a Schiff base compound;

[0028] (2) The Schiff base compound, 1,2-dichloroethane, and 4-bromo-3-mercaptobenzoic acid are mixed in a mass ratio of 1:6:0.9. After being placed in an ice bath and stirred at 60 rpm for 10 min, 4 times the mass of the Schiff base compound of Eaton reagent is added. After continuing to stir for 30 min, the ice bath is removed, and the product is continuously stirred at room temperature for 30 min. The product is placed in an oil bath, heated to 50℃, and reacted for 12 h. After cooling to room temperature, the product is extracted with water three times, and then the organic layer is extracted with saturated brine once, dried with anhydrous sodium sulfate for 1 h, filtered, concentrated at 60℃ under a vacuum of-0.06 MPa for 3 h, and dried at 80℃ for 24 h to obtain a benzophenone compound;

[0029] (3) The benzophenone compound, 10-alkenylundecyloxytrimethylsilane, dichloromethane, and triethylamine are mixed in a mass ratio of 1:0.5:7:0.08. After being reacted at room temperature for 6 h, the product is heated to 50℃ and reacted for 4 h to obtain an organosilicon compound;

[0030] (4) Cotton cellulose and a 64% mass fraction of sulfuric acid solution are mixed in a mass ratio of 1:15.5. After being stirred at 50℃ and 100 rpm for 1 h, 10 times the volume of the reaction solution of deionized water is added, and the product is centrifuged at 8000 rpm for 20 min. The product is placed in a dialysis bag with a molecular weight of 8000 and dialyzed with deionized water for 7 d to obtain pretreated cellulose. The pretreated cellulose, anhydrous tetrahydrofuran, triethylamine, 4-dimethylaminopyridine, and 2-bromoisobutyryl bromide solution are mixed in a mass ratio of 1:89:1.95:0.5:31.7. The mass ratio of 2-bromoisobutyryl bromide to anhydrous tetrahydrofuran in the 2-bromoisobutyryl bromide solution is 1:5.34. After being sealed and stirred at 60 rpm under a nitrogen atmosphere at 25℃ for 24 h, the product is centrifuged at 8000 rpm for 8 min with anhydrous ethanol, anhydrous tetrahydrofuran, and acetone, respectively, to obtain brominated cellulose;

[0031] (5) mixed brominated cellulose, N, N-dimethylformamide, hexamethylene diisocyanate according to mass ratio 1:5:0.5, stirred at 60℃ and 80rpm for 7h, then added N, N-dimethylformamide with 5 times the mass of brominated cellulose, and organic silicon compound with 0.5 times the mass of brominated cellulose, continued to stir at the same temperature for 12h, washed with deionized water for 6 times, dried at 90℃ and vacuum degree-0.08MPa for 24h to obtain modified cellulose;

[0032] (6) mixed gelatin aqueous solution with mass fraction of 0.5% and gum arabic aqueous solution with mass fraction of 0.5% according to volume ratio 1:1 to obtain wall material solution, added jasmine absolute oil according to core-wall ratio 1:1, stirred at 10000rpm for 3min, then decreased the water bath temperature to 40℃, stirred at 200rpm for 30min, added acetic acid to the solution pH 3.1, reacted for 30min, then decreased the temperature to 10℃, added sodium bicarbonate to the solution pH 6, added transglutaminase with 0.06 times the mass of wall material solution, continued to react for 4h, filtered, washed with deionized water by centrifugation for 3 times, dried at 60℃ for 24h to obtain fragrance microcapsule;

[0033] (7) mixed modified cellulose, fragrance microcapsule, N, N-dimethylacetamide according to mass ratio 1:0.2:5, stirred at 45℃ and 100rpm for 30min, then electrospun at 30℃, needle tip inner diameter 0.1mm, collection distance 15cm, electric field strength 1kV / cm, extrusion rate 0.02mL / min, then twisted at 20twist / 10cm to obtain 30dtex yarn; placed the yarn in dyeing solution according to bath ratio 1:20, the mass ratio of reactive dye and deionized water in the dyeing solution was 1:24, immersed for 10min, then taken out, placed in salt and alkali bath according to bath ratio 1:20, the salt and alkali bath included sodium sulfate 20g / L and sodium carbonate 40g / L, immersed at 55℃ for 3min, then taken out, fixed color at 100℃ steam for 8-10min, washed with cold water for 2 times, dried at 60℃ for 12h to obtain waterproof fragrance dyed yarn.

[0034] Example 2

[0035] (1) dispersed chitosan in methanol with 50 times the mass of chitosan, swelled for 1h, then increased the temperature to 45℃, added 2, 4-hydroxybenzaldehyde alcohol solution with 12.2 times the mass of chitosan, the mass ratio of 2, 4-hydroxybenzaldehyde and anhydrous ethanol in 2, 4-hydroxybenzaldehyde alcohol solution was 1:6, reacted for 11h, then suction filtered, washed with methanol and deionized water for 4 times in turn, added anhydrous ethanol with 18 times the mass of chitosan, extracted at 78℃ for 12h, then suction filtered, dried at 50℃ and vacuum degree-0.08MPa for 10h to obtain Schiff base compound;

[0036] (2) Schiff base compound, 1,2-dichloroethane, 4-bromo-3-mercaptobenzoic acid were mixed according to the mass ratio of 1:9:1.05, and placed in an ice bath under argon protection. After stirring at 70 rpm for 10 min, Eaton reagent was added in an amount of 4.5 times the mass of the Schiff base compound. After continuing to stir for 30 min, the ice bath was removed, and the stirring was continued at room temperature for 40 min. Then, the reaction was heated to 55°C in an oil bath, and reacted for 12 h. After cooling to room temperature, the organic layer was extracted with water three times, and then extracted with saturated brine once. The organic layer was dried over anhydrous sodium sulfate for 1 h, filtered, concentrated under vacuum at a vacuum degree of -0.06 MPa and at 60°C for 3.5 h, and then dried at 80°C for 24 h to obtain the benzophenone compound;

[0037] (3) The benzophenone compound, 10-alkenyl undecyloxy trimethyl silane, dichloromethane and triethylamine were mixed according to the mass ratio of 1:0.6:9:0.09, and reacted at room temperature for 8 h, and then heated to 50°C for 5.5 h to obtain the organosilicon compound;

[0038] (4) Cotton cellulose and a 64% sulfuric acid solution were mixed according to the mass ratio of 1:15.5, and stirred at 50°C and 100 rpm for 1.5 h. Then, deionized water was added in an amount of 10 times the volume of the reaction solution, and centrifuged at 8000 rpm for 25 min. The pretreated cellulose was placed in a dialysis bag with a molecular weight of 11000, and dialyzed with deionized water for 7 d to obtain the pretreated cellulose. The pretreated cellulose, anhydrous tetrahydrofuran, triethylamine, 4-dimethylaminopyridine and 2-bromoisobutyryl bromide solution were mixed according to the mass ratio of 1:89:1.95:0.5:31.7. The mass ratio of 2-bromoisobutyryl bromide to anhydrous tetrahydrofuran in the 2-bromoisobutyryl bromide solution was 1:5.34. The mixture was sealed and stirred at 25°C under a nitrogen atmosphere at 70 rpm for 24 h. Then, the mixture was centrifuged at 8000 rpm for 12 min with anhydrous ethanol, anhydrous tetrahydrofuran and acetone, respectively, to obtain the brominated cellulose;

[0039] (5) The brominated cellulose, N,N-dimethylformamide and hexamethylene diisocyanate were mixed according to the mass ratio of 1:5:0.5, and stirred at 60°C and 80 rpm for 7.5 h. Then, N,N-dimethylformamide was added in an amount of 6.5 times the mass of the brominated cellulose, and the organosilicon compound was added in an amount of 0.65 times the mass of the brominated cellulose. The mixture was continuously stirred at the same temperature for 13 h. Then, the mixture was washed with deionized water six times, and dried at a vacuum degree of -0.08 MPa and at 90°C for 24 h to obtain the modified cellulose;

[0040] (6) 50℃ water bath, 1.5% gelatin aqueous solution, 1.5% gum arabic aqueous solution mixed by volume ratio 1:1, wall material solution was obtained, the jasmine absolute oil was added by core wall ratio 1:2, 10000 rpm stirring for 4 min, the water bath temperature was reduced to 40℃, 500 rpm stirring for 30 min, then acetic acid was added until the solution pH was 3.7, after 35 min reaction, the temperature was reduced to 10℃, sodium bicarbonate was added until the solution pH was 6, 0.06 times wall material solution of transglutaminase was added, after 6 h continuous reaction, filtration, centrifugal washing with deionized water for 3 times, 60℃ drying for 24 h, the aromatic microcapsule was obtained;

[0041] (7) The modified cellulose, aromatic microcapsule and N,N-dimethylacetamide were mixed by mass ratio 1:0.35:5, 50℃, 100 rpm stirring for 45 min, then electrospinning was carried out at 30℃, the needle tip inner diameter was 0.1 mm, the collection distance was 18 cm, the electric field strength was 1.2 kV / cm, and the extrusion rate was 0.04 mL / min, then twisting was carried out at 30 twists / 10 cm, the 32 dtex yarn was obtained; the yarn was placed in the dyeing solution by bath ratio 1:20, the mass ratio of reactive dye and deionized water in the dyeing solution was 1:36.5, after 20 min immersion, the yarn was taken out and placed in the salt bath by bath ratio 1:20, the salt bath included sodium sulfate 25 g / L and sodium carbonate 45 g / L, after 4 min immersion at 60℃, the yarn was taken out, steam fixation was carried out at 102℃ for 9 min, then the yarn was washed with cold water for 3 times, and the waterproof aromatic dyed yarn was obtained after 12 h drying at 60℃.

[0042] Example 3

[0043] (1) Chitosan was dispersed in chitosan mass 60 times of methanol, swelling for 1 h, then the temperature was increased to 50℃, 2,4-hydroxybenzaldehyde alcohol solution was added, the mass ratio of 2,4-hydroxybenzaldehyde and anhydrous ethanol in the 2,4-hydroxybenzaldehyde alcohol solution was 1:6, after 12 h reaction, suction filtration was carried out, then methanol and deionized water were used for washing for 4 times, respectively, anhydrous ethanol was added, the mass of chitosan was 22 times, extraction was carried out at 82℃ for 12 h, then suction filtration was carried out, and the Schiff base compound was obtained after drying at 50℃ under vacuum degree-0.08 MPa for 10 h;

[0044] (2) Schiff base compound, 1,2-dichloroethane, 4-bromo-3-mercaptobenzoic acid were mixed in a mass ratio of 1:12:1.2, placed in an ice bath under argon protection, stirred at 80 rpm for 10 min, then added 5 times the mass of the Schiff base compound of Eaton reagent, continued to stir for 30 min, removed the ice bath, continued to stir at room temperature for 50 min, placed in an oil bath, warmed to 60℃, reacted for 12 h, cooled to room temperature, extracted with water 3 times, took the organic layer, extracted with saturated brine once, dried with anhydrous sodium sulfate for 1 h, filtered, concentrated under vacuum at-0.06 MPa, 60℃ for 4 h, then dried at 80℃ for 24 h to obtain the benzophenone compound;

[0045] (3) The benzophenone compound, 10-alkenyl undecyloxy trimethyl silane, dichloromethane, triethylamine were mixed in a mass ratio of 1:0.7:11:0.1, reacted at room temperature for 10 h, then warmed to 50℃ and reacted for 7 h to obtain the organosilicon compound;

[0046] (4) Cotton cellulose and a 64% sulfuric acid solution were mixed in a mass ratio of 1:15.5, stirred at 50℃ and 100 rpm for 2 h, then added 10 times the volume of deionized water to the reaction solution, centrifuged at 8000 rpm for 30 min, placed in a dialysis bag with a molecular weight of 14000, and dialyzed with deionized water for 7 d to obtain the pretreated cellulose; the pretreated cellulose, anhydrous tetrahydrofuran, triethylamine, 4-dimethylaminopyridine, and 2-bromoisobutyryl bromide solution were mixed in a mass ratio of 1:89:1.95:0.5:31.7, the mass ratio of 2-bromoisobutyryl bromide to anhydrous tetrahydrofuran in the 2-bromoisobutyryl bromide solution was 1:5.34, sealed and stirred at 25℃ under a nitrogen atmosphere at 80 rpm for 24 h, then centrifuged with anhydrous ethanol, anhydrous tetrahydrofuran and acetone at 8000 rpm for 15 min respectively to obtain the brominated cellulose;

[0047] (5) The brominated cellulose, N,N-dimethylformamide, and hexamethylene diisocyanate were mixed in a mass ratio of 1:5:0.5, stirred at 60℃ and 80 rpm for 8 h, then added 8 times the mass of the brominated cellulose of N,N-dimethylformamide and 0.8 times the mass of the brominated cellulose of the organosilicon compound, continued to stir at the same temperature for 14 h, washed with deionized water 6 times, dried at-0.08 MPa and 90℃ for 24 h to obtain the modified cellulose;

[0048] (6) Under a water bath at 50℃, a 2.5% gelatin aqueous solution and a 2.5% gum arabic aqueous solution were mixed at a volume ratio of 1:1 to obtain a wall material solution. Jasmine essential oil was added at a core-to-wall ratio of 1:3. After stirring at 10,000 rpm for 5 min, the water bath temperature was lowered to 40℃. After stirring at 800 rpm for 30 min, acetic acid was added until the solution pH was 4.3. After reacting for 40 min, the temperature was lowered to 10℃, sodium bicarbonate was added until the solution pH was 6, and transglutaminase was added at 0.06 times the mass of the wall material solution. After continuing to react for 8 h, the solution was filtered, washed three times by centrifugation with deionized water, and dried at 60℃ for 24 h to obtain aromatic microcapsules.

[0049] (7) Modified cellulose, aromatic microcapsules, and N,N-dimethylacetamide were mixed at a mass ratio of 1:0.5:5 and stirred at 55°C and 100 rpm for 60 min. Then, electrospinning was carried out at 30°C with a needle tip inner diameter of 0.1 mm, a collection distance of 20 cm, an electric field strength of 1.4 kV / cm, and an extrusion rate of 0.06 mL / min. The yarn was then twisted at 40 twists / 10 cm to obtain a 35 dtex yarn. The yarn was placed in a dyeing solution at a bath ratio of 1:20, with a mass ratio of reactive dye to deionized water of 1:49. After soaking for 30 min, the yarn was removed and placed in a salt-alkali bath at a bath ratio of 1:20, which included 30 g / L sodium sulfate and 50 g / L sodium carbonate. After soaking at 65°C for 5 min, the yarn was removed and steam-fixed at 105°C for 10 min. The yarn was washed three times with cold water and dried at 60°C for 12 h to obtain a waterproof aromatic dyed yarn.

[0050] Comparative Example 1

[0051] The difference between Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is changed to: 2,4-hydroxybenzaldehyde, 1,2-dichloroethane, and 4-bromo-3-mercaptobenzoic acid are mixed in a mass ratio of 1:9:1.05, placed in an ice bath under argon protection, stirred at 70 rpm for 10 min, then Eaton reagent of 4.5 times the mass of 2,4-hydroxybenzaldehyde is added, and stirring is continued for 30 min. The ice bath is removed, and stirring is continued at room temperature for 40 min. The mixture is then placed in an oil bath, heated to 55°C, and reacted for 12 h. After cooling to room temperature, the mixture is extracted three times with water, and the organic layer is taken. It is extracted once with saturated brine, dried with anhydrous sodium sulfate for 1 h, filtered, concentrated under vacuum of -0.06 MPa at 60°C for 3.5 h, and then dried at 80°C for 24 h to obtain the benzophenone compound. The remaining steps are the same as in Example 2.

[0052] Comparative Example 2

[0053] Comparative Example 2 is different from Example 2 in that step (2) is not included, and step (3) is changed to: mixing the benzophenone compound, 10-alkenyl undecyloxy trimethyl silane, dichloromethane, and triethylamine in a mass ratio of 1:0.6:9:0.09, and reacting at room temperature for 8 h, and then heating to 50 DEG C and reacting for 5.5 h to obtain the silicone compound. The remaining steps are the same as in Example 2.

[0054] Comparative Example 3

[0055] Comparative Example 3 is different from Example 2 in that step (3) is not included, and step (5) is changed to: mixing the cellulose bromide, N,N-dimethylformamide, and hexamethylene diisocyanate in a mass ratio of 1:5:0.5, stirring at 60 DEG C and 80 rpm for 7.5 h, then adding N,N-dimethylformamide in an amount of 6.5 times the mass of the cellulose bromide, and the silicone compound in an amount of 0.65 times the mass of the cellulose bromide, continuing to stir and react at the same temperature for 13 h, then washing with deionized water 6 times, and drying at a vacuum of -0.08 MPa and 90 DEG C for 24 h to obtain the modified cellulose. The remaining steps are the same as in Example 2.

[0056] Effect Example

[0057] The performance analysis results of the water-proof aromatic dyeing yarns using Examples 1 to 3 and Comparative Examples 1 to 3 of the present application are shown in Table 1 below.

[0058] Table 1

[0059]

[0060]

[0061] From the comparison of the experimental data of the examples and comparative examples, it can be found that the present application uses chitosan as an antibacterial raw material, reacts with 2,4-hydroxybenzaldehyde to form a Schiff base, improves the antibacterial activity of chitosan, thereby improving the antibacterial property of the yarn, then reacts with 4-bromo-3-mercaptobenzoic acid to form a benzophenone structure that can absorb ultraviolet light, thereby improving the ultraviolet resistance of the yarn, further reacts with 10-alkenyl undecyloxy trimethyl silane to introduce long-chain silane groups, thereby improving the water-proof effect of the yarn, and then uses the hydroxyl groups to graft to the cellulose bromide to obtain a modified cellulose, thereby further improving the performance of the yarn.

[0062] It will be apparent to those skilled in the art that the application is not limited to the details of the above-exemplified embodiments and that the present application can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. The embodiments should therefore be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the above description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. No reference herein to any prior art is to be taken as an admission that the present application is not entitled to antedate such prior art by virtue of prior application. Any reference to the term "comprising" is to be construed in accordance with the definition of that term provided in the preamble to Article 69 of the European Patent Convention. Any reference to the term "comprising" is to be construed in accordance with the definition of that term provided in the preamble to Article 69 of the European Patent Convention.

Claims

1. A waterproof, aromatic dyed yarn, characterized in that, The waterproof aromatic dyed yarn is made by spinning a mixture of aromatic microcapsules and modified cellulose, followed by dyeing treatment. The modified cellulose is prepared as follows: (1) Chitosan is dispersed in methanol at 40-60 times the weight of chitosan, swollen for 1 hour, heated to 40-50°C, and 2,4-hydroxybenzaldehyde alcohol solution at 9.0-15.4 times the weight of chitosan is added. After reacting for 10-12 hours, the mixture is filtered and washed 4 times with methanol and deionized water. Anhydrous ethanol at 14-22 times the weight of chitosan is added, and the mixture is extracted at 75-82°C for 12 hours. After filtration, the mixture is dried at 50°C and vacuum degree of -0.08MPa for 10 hours to obtain Schiff base compound. (2) Schiff base compound, 1,2-dichloroethane and 4-bromo-3-mercaptobenzoic acid were mixed in a mass ratio of 1:6:0.9~1:12:1.

2. Under argon protection, the mixture was placed in an ice bath and stirred at 60~80 rpm for 10 min. Then, Eaton reagent of 4~5 times the mass of Schiff base compound was added and stirred for another 30 min. The ice bath was removed and the mixture was stirred at room temperature for another 30~50 min. The mixture was then placed in an oil bath and heated to 50~60℃. After reacting for 12 h, the mixture was cooled to room temperature and extracted three times with water. The organic layer was extracted once with saturated brine and dried with anhydrous sodium sulfate for 1 h. The mixture was filtered and concentrated at 60℃ under a vacuum of -0.06 MPa for 3~4 h. Finally, it was dried at 80℃ for 24 h to obtain benzophenone compound. (3) Mix benzophenone compound, 10-enylundecyloxytrimethylsilane, dichloromethane and triethylamine in a mass ratio of 1:0.5:7:0.08~1:0.7:11:0.1, react at room temperature for 6~10h, then heat to 50℃ and react for 4~7h to obtain organosilicon compound; (4) The pretreated cellulose, anhydrous tetrahydrofuran, triethylamine, 4-dimethylaminopyridine, and 2-bromoisobutyryl bromide solution were mixed in a mass ratio of 1:89:1.95:0.5:31.7, sealed, and stirred at 60-80 rpm for 24 h at 25 °C under a nitrogen atmosphere. Then, the mixture was centrifuged at 8000 rpm for 8-15 min with anhydrous ethanol, anhydrous tetrahydrofuran, and acetone, respectively, to obtain brominated cellulose. (5) Mix cellulose bromide, N,N-dimethylformamide and hexamethylene diisocyanate in a mass ratio of 1:5:0.5, stir at 60°C and 80 rpm for 7-8 h, add N,N-dimethylformamide at 5-8 times the mass of cellulose bromide and organosilicon compound at 0.5-0.8 times the mass of cellulose bromide, continue stirring at the same temperature for 12-14 h, wash with deionized water 6 times, dry at -0.08 MPa and 90°C for 24 h to obtain modified cellulose.

2. The waterproof aromatic dyed yarn according to claim 1, characterized in that, The 2,4-hydroxybenzaldehyde alcohol solution in step (1) is a mixture of 2,4-hydroxybenzaldehyde and anhydrous ethanol at a mass ratio of 1:

6.

3. The waterproof aromatic dyed yarn according to claim 1, characterized in that, The preparation method of the pretreated fiber in step (4) is as follows: cotton cellulose and sulfuric acid solution with a mass fraction of 64% are mixed at a mass ratio of 1:15.

5. After stirring at 50℃ and 100rpm for 1-2 hours, deionized water with a volume of 10 times the reaction liquid is added. After centrifugation at 8000rpm for 20-30 minutes, the mixture is placed in a dialysis bag with a molecular weight of 8000-14000 and dialyzed with deionized water for 7 days to obtain pretreated cellulose.

4. The waterproof aromatic dyed yarn according to claim 1, characterized in that, The 2-bromoisobutyryl bromide solution in step (4) is a mixture of 2-bromoisobutyryl bromide and anhydrous tetrahydrofuran at a mass ratio of 1:5.

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5. The waterproof aromatic dyed yarn according to claim 1, characterized in that, The waterproof aromatic dyed yarn comprises the following preparation steps: Modified cellulose, aromatic microcapsules, and N,N-dimethylacetamide are mixed at a mass ratio of 1:0.2:5 to 1:0.5:5, stirred at 45-55℃ and 100 rpm for 30-60 minutes, then electrospun, and twisted at 20-40 twists / 10cm to obtain a yarn of 30-35 dtex; the yarn is placed in a dyeing solution at a bath ratio of 1:20, where the mass ratio of reactive dye to deionized water is 1:24 to 1:49, and immersed for 10-30 minutes. After immersion, the yarn is placed in a salt-alkali bath at a bath ratio of 1:20, immersed at 55-65℃ for 3-5 minutes, then removed and steam-fixed at 100-105℃ for 8-10 minutes. The yarn is then washed 2-3 times with cold water and dried at 60℃ for 12 hours to obtain the waterproof aromatic dyed yarn.

6. The waterproof aromatic dyed yarn according to claim 5, characterized in that, The method for preparing the aromatic microcapsules is as follows: A gelatin aqueous solution with a mass fraction of 0.5-2.5% and a gum arabic aqueous solution with a mass fraction of 0.5-2.5% are mixed at a volume ratio of 1:1 in a 50°C water bath to obtain a wall material solution. Jasmine essential oil is added at a core-to-wall ratio of 1:1-1:

3. After stirring at 10,000 rpm for 3-5 minutes, the water bath temperature is lowered to 40°C, and the mixture is stirred at 200-800 rpm for 30 minutes. Acetic acid is added until the pH of the solution is 3.1-4.3, and the reaction is continued for 30-40 minutes. The temperature is then lowered to 10°C, and sodium bicarbonate is added until the pH of the solution is 6. Transglutaminase is added at a mass ratio of 0.06 times that of the wall material solution. The reaction is continued for 4-8 hours. After filtration, the mixture is washed three times by centrifugation with deionized water and dried at 60°C for 24 hours to obtain the aromatic microcapsules.

7. The waterproof aromatic dyed yarn according to claim 5, characterized in that, The spinning conditions are: 30℃, needle tip inner diameter of 0.1mm, collection distance of 15~20cm, electric field strength of 1.0~1.4kV / cm, and extrusion rate of 0.02~0.06mL / min; the salt-alkali bath consists of sodium sulfate of 20~30g / L and sodium carbonate of 40~50g / L.

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