Production process of natural aromatic acetate fiber fabric

Abstract

The application discloses a production process of natural fragrance-containing acetate fabric, and the acetate fabric is prepared through dry spinning of a solvent prepared by mixing modified polymer, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, modified microcapsule and dimethylformamide, wherein the weight ratio of the modified polymer and the modified microcapsule is 70-80:6-8. The modified polymer is prepared by using excessive isocyanate groups on hexamethylene diisocyanate as reaction sites, first reacting with an intermediate containing dihydroxy, and then reacting with cellulose acetate containing free hydroxyl. The halogen amine structure on the molecular chain can destroy the cell membrane, enzyme system or genetic material through oxidation. The modified capsule has a double-component double-wall structure of lavender essential oil and cinnamon essential oil, which can improve the fragrance persistence, and the copper sulfide nanoparticles and the quaternized chitosan structure can destroy the bacterial cell structure and improve the antibacterial performance of the material.

Description

Technical Field

[0001] This invention relates to the field of acetate fiber production processes, specifically to a production process for acetate fiber fabrics containing natural aromas. Background Technology

[0002] With the improvement of people's living standards, consumers have increasingly stringent and diversified requirements for clothing, which has injected new impetus into the rapid development of functional aromatic textiles. Functional aromatic textiles incorporate fragrances into fabrics in a certain way, improving people's physical and mental health while increasing the added value of textiles. However, obtaining high-value-added functional textiles that are green, safe, low-cost, have a long-lasting fragrance, and are durable and washable remains a significant challenge. The purpose of this invention is to prepare an acetate fiber fabric containing natural fragrance. This fabric possesses both antibacterial and fragrance properties; its antibacterial properties effectively inhibit the growth of bacteria on clothing, preventing bacterial infections of human skin and protecting human health; its fragrance can physiologically and psychologically relieve stress, improve sleep quality, and can be combined with medication to treat related diseases. Summary of the Invention

[0003] The purpose of this invention is to provide a production process for acetate fiber fabric containing natural fragrance, which solves the problems of poor antibacterial properties and short-lasting fragrance of current acetate fiber fabrics.

[0004] The objective of this invention can be achieved through the following technical solutions: A production process for acetate fiber fabric containing natural fragrance specifically includes the following steps: Step S1: Mix the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules and dimethylformamide evenly to prepare a spinning solution. Dry spin the fiber at a winding speed of 500-700 m / min and a tunnel hot air temperature of 120-160℃, and then irradiate it with ultraviolet light to obtain pretreated fibers. The pretreated fabric is obtained by knitting. Step S2: Place the pretreated fabric in a sodium hypochlorite solution, adjust the pH of the solution to 7, immerse it at 20-30℃ for 50-60 minutes, wash it, and dry it at 45℃ for 60 minutes to obtain an acetate fiber fabric with natural fragrance.

[0005] Further, in step S1, the weight ratio of the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules, and dimethylformamide is 70-80:0.3-0.6:6-8:100-120, and the weight of the pretreated fabric is 100-110 g / m². 2 .

[0006] Furthermore, the sodium hypochlorite solution in step S2 has a mass concentration of 300 g / L and an active chlorine content of ≥5.3%.

[0007] Furthermore, the modified polymer is prepared by the following steps: Step A1: Mix 5,5-dimethylhydantoin, ethanol, and sodium hydroxide evenly. Stir and add 3-chloro-1,2-propanediol under the conditions of 100-120 r / min, 20-30℃, and pH 9.5-10, and react for 8-10 h to obtain intermediate 1. Mix 3-mercapto-1,2-propanediol, acetonitrile, and tert-butyl disulfide evenly. Stir and add triethylamine under the conditions of 110-130 r / min, 0-20℃, and nitrogen gas, and react for 2-3 h to obtain intermediate 2. Step A2: Mix hexamethylene diisocyanate, dimethylformamide, dibutyltin disilicate, intermediate 1 and intermediate 2 evenly, and react for 2-4 hours at a speed of 150-170 r / min and a temperature of 50-70℃. Stir and add cellulose acetate and triethylamine, and react for 30-50 minutes to obtain the pretreated polymer. Step A3: Mix the pretreated polymer, tetrahydrofuran and deionized water evenly, stir and add tris(2-carboxyethyl)phosphine hydrochloride at a speed of 100-120 r / min and a temperature of 20-30℃, and react for 2-4 h to obtain the modified polymer.

[0008] Furthermore, in step A1, the ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloro-1,2-propanediol is 1 mmol:1 mmol:1.1 mmol, and the ratio of 3-mercapto-1,2-propanediol, tert-butyl disulfide, and triethylamine is 1 mmol:1.2 mmol:1.1 mmol.

[0009] Further, in step A2, the ratio of hexamethylene diisocyanate, intermediate 1, intermediate 2, and cellulose acetate is 1 mol: 0.2-0.3 mol: 0.2-0.3 mol: 0.8-1 mol, the degree of esterification of cellulose acetate is 200-260, the content of bound acetic acid is 48.8-58.8%, the amount of dibutyltin dibutylsilicate is 0.05-0.1% of the mass of hexamethylene diisocyanate, and the amount of triethylamine is 0.1-0.3% of the mass of hexamethylene diisocyanate.

[0010] Furthermore, the molar ratio of disulfide bonds and tris(2-carboxyethyl)phosphine hydrochloride on the pretreated polymer in step A3 is 1:1.5-2.

[0011] Furthermore, the modified microcapsules are prepared by the following steps: Step B1: Mix bromopropylene, acetonitrile and isonicotinic acid evenly, and react for 6-8 hours at a speed of 90-110 r / min and a temperature of 80-90℃ to obtain intermediate 3. Mix intermediate 3 and N-hydroxysuccinimide evenly, and stir and add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water at a speed of 100-120 r / min and a temperature of 20-30℃, and react for 1-2 hours. Add acetic acid solution of chitosan and react for 20-24 hours to obtain quaternized chitosan. Step B2: Mix copper sulfate pentahydrate, deionized water, and ammonia water evenly, and react for 20-30 minutes at a speed of 110-130 r / min and a temperature of 20-30℃. Stir and add quaternized chitosan, and react for 1-2 hours. Raise the temperature to 65-75℃, add sodium sulfide nonahydrate, and react for 40-50 minutes to obtain a modified wall material. Mix cinnamon essential oil, Tween 80, and deionized water evenly, and shear at high speed for 10-15 minutes at a speed of 6000-7000 r / min and a temperature of 20-30℃ to obtain a cinnamon flavor emulsion. Mix the cinnamon flavor emulsion and gum arabic aqueous solution evenly, and stir for 40-50 minutes at a speed of 4000-6000 r / min to obtain a single-capsule wall cinnamon flavor microcapsule emulsion. Step B3: Mix lavender essential oil, Tween 80, and deionized water evenly. Under high-speed shearing conditions of 6000-7000 r / min and 20-30℃, obtain lavender fragrance emulsion. Mix lavender fragrance emulsion and gum arabic aqueous solution evenly. Under high-speed stirring conditions of 4000-6000 r / min, obtain single-cell wall lavender microcapsule emulsion. Mix single-cell wall cinnamon microcapsule emulsion and single-cell wall lavender microcapsule emulsion evenly. Under high-speed stirring conditions of 120-130 r / min, add modified wall material aqueous solution to obtain modified microcapsules.

[0012] Further, in step B1, the molar ratio of bromopropene and isonicotinic acid is 1.1:1, and the volume ratio of intermediate 3, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, deionized water, and the acetic acid solution of chitosan is 5 mmol:4.2 mmol:4.2 mmol:20 mL:50 mL. The acetic acid solution of chitosan is prepared by adding 2 mmol of chitosan to 50 mL of a 2% (w / w) acetic acid solution.

[0013] Furthermore, in step B2, the ratio of copper sulfate pentahydrate, deionized water, ammonia, quaternized chitosan, and sodium sulfide nonahydrate is 0.1g:30mL:4mL:0.1g:0.2g, the molar concentration of ammonia is 7mol / L, the ratio of cinnamon essential oil, Tween 80, and deionized water is 1g:0.5-1g:6-8mL, the ratio of cinnamon flavor emulsion and gum arabic aqueous solution is 1mL:1.5mL, and the mass fraction of gum arabic aqueous solution is 1%.

[0014] Furthermore, in step B3, the ratio of lavender essential oil, Tween 80, and deionized water is 1g:0.5-1g:6-8mL; the ratio of lavender fragrance emulsion to gum arabic aqueous solution is 1mL:1.5mL; the mass fraction of gum arabic aqueous solution is 1%; and the ratio of single-cell wall cinnamon microcapsule emulsion, single-cell wall lavender microcapsule emulsion, and modified wall material aqueous solution is 1mL:1mL:1.5-2mL; the mass fraction of modified wall material aqueous solution is 1%.

[0015] The beneficial effects of this invention are as follows: A spinning solution is prepared by mixing a modified polymer, modified microcapsules, and dimethylformamide components in a specific ratio, and fibers are produced through a dry spinning process. Under ultraviolet irradiation and the action of an initiator, the thiol groups on the modified polymer molecules react with the carbon-carbon double bonds on the modified microcapsule molecules to obtain a pretreated fabric. The fabric is then immersed in a sodium hypochlorite solution for chlorination treatment of the cyclic imides in the molecular chain, forming a chloramine structure, thus obtaining an acetate fiber fabric containing natural aroma.

[0016] Modified polymer: 5,5-Dimethylhydantoin is a cyclic imide. Under alkaline conditions, the hydrogen atom on the first nitrogen atom of its imide is removed, forming a nitrogen anion. This nitrogen anion then nucleophilically attacks the carbon atom attached to the chlorine atom in the 3-chloro-1,2-propanediol molecule, making the chloride ion a leaving group. Simultaneously, by controlling the material ratio and alkaline environment, the dialkylation reaction is suppressed, yielding intermediate 1. Under the action of a catalyst, 3-mercapto-1,2-propanediol undergoes a thiol and disulfide bond exchange reaction with the symmetrical disulfide compound tert-butyldisulfide, protecting the thiol group, yielding intermediate 2. Under the action of a catalyst, the two isocyanate groups on the hexamethylene diisocyanate molecule react with the terminal hydroxyl groups on intermediates 1 and 2 to form urethane bonds. Then, the remaining isocyanate groups react with the incompletely acetylated free hydroxyl groups on the cellulose acetate chain, yielding the pretreated polymer. The modified polymer was prepared by selectively reducing and cleaving the tert-butyl disulfide protecting group introduced in intermediate 2 to form a mercapto group using tri(2-carboxyethyl)phosphonic acid hydrochloride, a highly efficient disulfide bond reducing agent.

[0017] Modified microcapsules: The nitrogen atom on the pyridine ring of isonicotinic acid has a lone pair of electrons, which are nucleophilically replaced by the bromine atom of bromopropene under heating conditions, undergoing an alkylation reaction to generate a quaternary ammonium salt structure, thus preparing intermediate 3. The carboxyl group on the aromatic ring of intermediate 3 is activated and reacts with the amino group on chitosan to generate an amide structure, thus preparing quaternized chitosan. Copper sulfate pentahydrate dissolves in water to form hydrated copper ions. Adding excess ammonia water forms a copper-ammonia complex structure, which forms coordinate bonds with the amino and hydroxyl groups on the quaternized chitosan molecular chain, thereby fixing the copper ions on the molecular chain. Sodium sulfide nonahydrate ionizes in water to release sulfide ions, which are then used to synthesize copper sulfide nanoparticles in situ with the copper ions coordinated with the quaternized chitosan, thus preparing modified wall materials. Cinnamon essential oil is uniformly dispersed in an aqueous phase using the stabilizing effect of surfactants and the dispersing effect of high-speed shear forces to form an "oil-in-water emulsion," thus producing a cinnamon fragrance emulsion. An aqueous solution of gum arabic is then added, and under the influence of electrostatic and hydrogen bonding, gum arabic acts as a wall material adsorbed onto the surface of the cinnamon fragrance emulsion, resulting in a single-walled cinnamon fragrance microcapsule emulsion. Similarly, lavender essential oil is uniformly dispersed in an aqueous phase to produce a lavender fragrance emulsion, and an aqueous solution of gum arabic is added to form a single-walled lavender microcapsule emulsion. When a positively charged modified wall material aqueous solution is added to a mixture of negatively charged single-walled cinnamon fragrance microcapsule emulsions and single-walled lavender microcapsule emulsions, the positive and negative charges attract and neutralize each other. Through complex coagulation, the modified wall material encapsulates the two-component single-walled microcapsules, forming a second layer of capsule wall, thus producing modified microcapsules.

[0018] The pre-treated fabric undergoes sodium hypochlorite impregnation, introducing a halogenated amine structure into its molecular chain. Upon contact with microorganisms, the NX bonds on this structure can destroy cell membranes, enzyme systems, or genetic material through oxidation, effectively targeting pathogens such as bacteria, fungi, and viruses. Furthermore, it achieves high-efficiency sterilization even at low concentrations, reducing potential side effects on the environment and human body. After killing bacteria, the halogenated amine reverts to its imide-containing precursor, reacting with donor compounds that can provide Cl, Br, or I, such as sodium hypochlorite, sodium hypobromite, and trichloroisocyanuric acid, to regenerate the halogenated amine structure, thus "regenerating" its antibacterial function. Utilizing microencapsulation technology, a dual-component, double-walled structure of lavender and cinnamon essential oils is formed on the modified capsules. By controlling the release rate of each component, multiple fragrances can be produced, enabling aromatic textiles to simultaneously achieve therapeutic effects such as aiding sleep, stabilizing emotions, and providing antibacterial and antifungal properties. The double-walled microcapsules, with their two-layered walls, exhibit enhanced density and resistance to breakage, significantly improving the shelf life of fragrances and enhancing their aroma retention, durability, and stability. The outermost quaternized chitosan wall material synergistically disrupts bacterial cell structures through the halogenated amine structure on the molecular chain, thus providing synergistic antibacterial effects. Copper sulfide nanoparticles efficiently absorb near-infrared light and convert it into heat, rapidly raising the fabric surface temperature within minutes to a level sufficient to destroy bacterial cell structures, leading to bacterial protein denaturation and membrane disruption, thereby enhancing the fabric's antibacterial properties. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1: A production process for acetate fiber fabric containing natural fragrance, specifically including the following steps: Step S1: Mix the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules and dimethylformamide evenly to prepare a spinning solution. Dry spin the solution at a winding speed of 500 m / min and a tunnel hot air temperature of 120°C. Then, irradiate the solution with ultraviolet light to obtain pretreated fibers. Knit the pretreated fabric. Step S2: Place the pretreated fabric in a sodium hypochlorite solution, adjust the pH of the solution to 7, immerse it at 20°C for 50 minutes, wash it, and dry it at 45°C for 60 minutes to obtain an acetate fiber fabric with natural fragrance.

[0021] The weight ratio of the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules, and dimethylformamide in step S1 is 70:0.3:6:100, and the weight of the pretreated fabric is 100 g / m². 2 .

[0022] The sodium hypochlorite solution in step S2 has a mass concentration of 300 g / L and an active chlorine content of ≥5.3%.

[0023] The modified polymer is prepared by the following steps: Step A1: Mix 5,5-dimethylhydantoin, ethanol and sodium hydroxide evenly, stir and add 3-chloro-1,2-propanediol under the conditions of 100 r / min, 20℃ and pH 9.5, and react for 8 h to obtain intermediate 1. Mix 3-mercapto-1,2-propanediol, acetonitrile and tert-butyl disulfide evenly, stir and add triethylamine under the conditions of 110 r / min, 0℃ and nitrogen gas, and react for 2 h to obtain intermediate 2. Step A2: Mix hexamethylene diisocyanate, dimethylformamide, dibutyltin disilicate, intermediate 1 and intermediate 2 evenly, and react for 2 hours at a speed of 150 r / min and a temperature of 50℃. Stir and add cellulose acetate and triethylamine, and react for 30 minutes to obtain the pretreated polymer. Step A3: Mix the pretreated polymer, tetrahydrofuran and deionized water evenly, stir and add tris(2-carboxyethyl)phosphine hydrochloride at a speed of 100 r / min and a temperature of 20℃, and react for 2 h to obtain the modified polymer.

[0024] In step A1, the ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloro-1,2-propanediol is 1 mmol:1 mmol:1.1 mmol, and the ratio of 3-mercapto-1,2-propanediol, tert-butyl disulfide, and triethylamine is 1 mmol:1.2 mmol:1.1 mmol.

[0025] In step A2, the ratio of hexamethylene diisocyanate, intermediate 1, intermediate 2, and cellulose acetate is 1 mol: 0.2 mol: 0.2 mol: 0.8 mol. The amount of hexamethylene diisocyanate is 1 mol, the degree of esterification of cellulose acetate is 200, the content of bound acetic acid is 48.8%, the amount of dibutyltin dibutylsilicate is 0.05% of the mass of hexamethylene diisocyanate, and the amount of triethylamine is 0.1% of the mass of hexamethylene diisocyanate.

[0026] The molar ratio of disulfide bonds and tris(2-carboxyethyl)phosphine hydrochloride on the pretreated polymer in step A3 is 1:1.5.

[0027] The modified microcapsules are prepared by the following steps: Step B1: Bromopropylene, acetonitrile and isonicotinic acid are mixed evenly and reacted at 90 r / min and 80 °C for 6 h to obtain intermediate 3. Intermediate 3 and N-hydroxysuccinimide are mixed evenly and stirred at 100 r / min and 20 °C. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water are added and reacted for 1 h. Then, an acetic acid solution of chitosan is added and reacted for 20 h to obtain quaternized chitosan. Step B2: Mix copper sulfate pentahydrate, deionized water, and ammonia water evenly, and react for 20 minutes at 110 r / min and 20°C. Stir and add quaternized chitosan, and react for 1 hour. Raise the temperature to 65°C, add sodium sulfide nonahydrate, and react for 40 minutes to obtain the modified wall material. Mix cinnamon essential oil, Tween 80, and deionized water evenly, and shear at high speed for 10 minutes at 6000 r / min and 20°C to obtain cinnamon flavor emulsion. Mix the cinnamon flavor emulsion and gum arabic aqueous solution evenly, and stir for 40 minutes at 4000 r / min to obtain single-capsule wall cinnamon flavor microcapsule emulsion. Step B3: Mix lavender essential oil, Tween 80, and deionized water evenly, and shear at high speed for 10 minutes at 6000 r / min and 20℃ to obtain lavender fragrance emulsion. Mix the lavender fragrance emulsion and gum arabic aqueous solution evenly, and stir at 4000 r / min for 40 minutes to obtain single-cell wall lavender microcapsule emulsion. Mix the single-cell wall cinnamon microcapsule emulsion and the single-cell wall lavender microcapsule emulsion evenly, stir at 120 r / min, and add modified wall material aqueous solution to obtain modified microcapsules.

[0028] In step B1, the molar ratio of bromopropene and isonicotinic acid is 1.1:1. The volume ratio of intermediate 3, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, deionized water, and acetic acid solution of chitosan is 5 mmol:4.2 mmol:4.2 mmol:20 mL:50 mL. The acetic acid solution of chitosan is prepared by adding 2 mmol of chitosan to 50 mL of 2% acetic acid solution.

[0029] In step B2, the ratio of copper sulfate pentahydrate, deionized water, ammonia, quaternized chitosan, and sodium sulfide nonahydrate is 0.1g:30mL:4mL:0.1g:0.2g, the molar concentration of ammonia is 7mol / L, the ratio of cinnamon essential oil, Tween 80, and deionized water is 1g:0.5g:6mL, the ratio of cinnamon flavor emulsion and gum arabic aqueous solution is 1mL:1.5mL, and the mass fraction of gum arabic aqueous solution is 1%.

[0030] In step B3, the ratio of lavender essential oil, Tween 80, and deionized water is 1g:0.5g:6mL; the ratio of lavender fragrance emulsion and gum arabic aqueous solution is 1mL:1.5mL; the mass fraction of gum arabic aqueous solution is 1%; and the ratio of single-cell wall cinnamon microcapsule emulsion, single-cell wall lavender microcapsule emulsion, and modified wall material aqueous solution is 1mL:1mL:1.5mL; the mass fraction of modified wall material aqueous solution is 1%.

[0031] Example 2: A production process for acetate fiber fabric containing natural fragrance, specifically including the following steps: Step S1: Mix the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules and dimethylformamide evenly to prepare a spinning solution. Dry spin the solution at a winding speed of 600 m / min and a tunnel hot air temperature of 140°C. Then, irradiate the solution with ultraviolet light to obtain pretreated fibers. Knit the pretreated fabric. Step S2: Place the pretreated fabric in a sodium hypochlorite solution, adjust the pH of the solution to 7, immerse it at 25°C for 55 minutes, wash it, and dry it at 45°C for 60 minutes to obtain an acetate fiber fabric with natural fragrance.

[0032] The weight ratio of the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules, and dimethylformamide in step S1 is 75:0.4:7:110, and the weight of the pretreated fabric is 100 g / m². 2 .

[0033] The sodium hypochlorite solution in step S2 has a mass concentration of 300 g / L and an active chlorine content of ≥5.3%.

[0034] The modified polymer is prepared by the following steps: Step A1: Mix 5,5-dimethylhydantoin, ethanol and sodium hydroxide evenly, stir and add 3-chloro-1,2-propanediol under the conditions of 110 r / min, 25℃ and pH 9.5, and react for 8 h to obtain intermediate 1. Mix 3-mercapto-1,2-propanediol, acetonitrile and tert-butyl disulfide evenly, stir and add triethylamine under the conditions of 120 r / min, 10℃ and nitrogen gas, and react for 2 h to obtain intermediate 2. Step A2: Mix hexamethylene diisocyanate, dimethylformamide, dibutyltin disilicate, intermediate 1 and intermediate 2 evenly, and react for 3 hours at a speed of 160 r / min and a temperature of 60℃. Stir and add cellulose acetate and triethylamine, and react for 40 minutes to obtain the pretreated polymer. Step A3: Mix the pretreated polymer, tetrahydrofuran and deionized water evenly, stir and add tris(2-carboxyethyl)phosphine hydrochloride at a speed of 110 r / min and a temperature of 25°C, and react for 3 h to obtain the modified polymer.

[0035] In step A1, the ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloro-1,2-propanediol is 1 mmol:1 mmol:1.1 mmol, and the ratio of 3-mercapto-1,2-propanediol, tert-butyl disulfide, and triethylamine is 1 mmol:1.2 mmol:1.1 mmol.

[0036] In step A2, the ratio of hexamethylene diisocyanate, intermediate 1, intermediate 2, and cellulose acetate is 1 mol: 0.2 mol: 0.2 mol: 0.8-1 mol, the amount of hexamethylene diisocyanate is 1.1 mol, the degree of esterification of cellulose acetate is 230, the bound acetic acid content is 50%, the amount of dibutyltin dibutylsilicate is 0.08% of the mass of hexamethylene diisocyanate, and the amount of triethylamine is 0.2% of the mass of hexamethylene diisocyanate.

[0037] The molar ratio of disulfide bonds and tris(2-carboxyethyl)phosphine hydrochloride on the pretreated polymer in step A3 is 1:1.6.

[0038] The modified microcapsules are prepared by the following steps: Step B1: Bromopropylene, acetonitrile and isonicotinic acid are mixed evenly and reacted at 100 r / min and 85 ℃ for 7 h to obtain intermediate 3. Intermediate 3 and N-hydroxysuccinimide are mixed evenly and stirred at 110 r / min and 25 ℃. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water are added and reacted for 1 h. Then, an acetic acid solution of chitosan is added and reacted for 22 h to obtain quaternized chitosan. Step B2: Mix copper sulfate pentahydrate, deionized water, and ammonia water evenly, and react for 25 minutes at 120 r / min and 25°C. Stir and add quaternized chitosan, and react for 1 hour. Raise the temperature to 70°C, add sodium sulfide nonahydrate, and react for 45 minutes to obtain the modified wall material. Mix cinnamon essential oil, Tween 80, and deionized water evenly, and shear at high speed for 12 minutes at 6000 r / min and 25°C to obtain cinnamon flavor emulsion. Mix the cinnamon flavor emulsion and gum arabic aqueous solution evenly, and stir for 45 minutes at 5000 r / min to obtain single-capsule wall cinnamon flavor microcapsule emulsion. Step B3: Mix lavender essential oil, Tween 80, and deionized water evenly, and shear at high speed for 12 minutes at 6000 r / min and 5℃ to obtain lavender fragrance emulsion. Mix the lavender fragrance emulsion and gum arabic aqueous solution evenly, and stir at 5000 r / min for 45 minutes to obtain single-cell wall lavender microcapsule emulsion. Mix the single-cell wall cinnamon microcapsule emulsion and the single-cell wall lavender microcapsule emulsion evenly, stir at 125 r / min, and add modified wall material aqueous solution to obtain modified microcapsules.

[0039] In step B1, the molar ratio of bromopropene and isonicotinic acid is 1.1:1. The volume ratio of intermediate 3, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, deionized water, and acetic acid solution of chitosan is 5 mmol:4.2 mmol:4.2 mmol:20 mL:50 mL. The acetic acid solution of chitosan is prepared by adding 2 mmol of chitosan to 50 mL of 2% acetic acid solution.

[0040] In step B2, the ratio of copper sulfate pentahydrate, deionized water, ammonia, quaternized chitosan, and sodium sulfide nonahydrate is 0.1g:30mL:4mL:0.1g:0.2g, the molar concentration of ammonia is 7mol / L, the ratio of cinnamon essential oil, Tween 80, and deionized water is 1g:0.6g:7mL, the ratio of cinnamon flavor emulsion and gum arabic aqueous solution is 1mL:1.5mL, and the mass fraction of gum arabic aqueous solution is 1%.

[0041] In step B3, the ratio of lavender essential oil, Tween 80, and deionized water is 1g:0.6g:7mL; the ratio of lavender fragrance emulsion and gum arabic aqueous solution is 1mL:1.5mL; the mass fraction of gum arabic aqueous solution is 1%; and the ratio of single-cell wall cinnamon microcapsule emulsion, single-cell wall lavender microcapsule emulsion, and modified wall material aqueous solution is 1mL:1mL:1.5mL; the mass fraction of modified wall material aqueous solution is 1%.

[0042] Example 3: A production process for acetate fiber fabric containing natural fragrance, specifically including the following steps: Step S1: Mix the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules and dimethylformamide evenly to prepare a spinning solution. Dry spin the solution at a winding speed of 700 m / min and a tunnel hot air temperature of 160°C. Then irradiate the solution with ultraviolet light to obtain pretreated fibers. Knit the pretreated fabric. Step S2: Place the pretreated fabric in a sodium hypochlorite solution, adjust the pH of the solution to 7, immerse it at 30°C for 60 minutes, wash it, and dry it at 45°C for 60 minutes to obtain an acetate fiber fabric with natural fragrance.

[0043] The weight ratio of the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules, and dimethylformamide in step S1 is 80:0.6:8:120, and the weight of the pretreated fabric is 110 g / m². 2 .

[0044] The sodium hypochlorite solution in step S2 has a mass concentration of 300 g / L and an active chlorine content of ≥5.3%.

[0045] The modified polymer is prepared by the following steps: Step A1: Mix 5,5-dimethylhydantoin, ethanol and sodium hydroxide evenly, stir and add 3-chloro-1,2-propanediol under the conditions of 120 r / min, 30℃ and pH 10, and react for 10 h to obtain intermediate 1. Mix 3-mercapto-1,2-propanediol, acetonitrile and tert-butyl disulfide evenly, stir and add triethylamine under the conditions of 130 r / min, 20℃ and nitrogen gas, and react for 3 h to obtain intermediate 2. Step A2: Mix hexamethylene diisocyanate, dimethylformamide, dibutyltin disilicate, intermediate 1 and intermediate 2 evenly, and react for 4 hours at a speed of 170 r / min and a temperature of 70℃. Stir and add cellulose acetate and triethylamine, and react for 50 minutes to obtain the pretreated polymer. Step A3: Mix the pretreated polymer, tetrahydrofuran and deionized water evenly, stir and add tris(2-carboxyethyl)phosphine hydrochloride at a speed of 120 r / min and a temperature of 30 °C, and react for 4 h to obtain the modified polymer.

[0046] In step A1, the ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloro-1,2-propanediol is 1 mmol:1 mmol:1.1 mmol, and the ratio of 3-mercapto-1,2-propanediol, tert-butyl disulfide, and triethylamine is 1 mmol:1.2 mmol:1.1 mmol.

[0047] In step A2, the ratio of hexamethylene diisocyanate, intermediate 1, intermediate 2, and cellulose acetate is 1 mol: 0.3 mol: 0.3 mol: 0.8-1 mol. The amount of hexamethylene diisocyanate is 1.3 mol, the degree of esterification of cellulose acetate is 260, the content of bound acetic acid is 58.8%, the amount of dibutyltin dibutylsilicate is 0.1% of the mass of hexamethylene diisocyanate, and the amount of triethylamine is 0.3% of the mass of hexamethylene diisocyanate.

[0048] The molar ratio of disulfide bonds and tris(2-carboxyethyl)phosphine hydrochloride on the pretreated polymer in step A3 is 1:2.

[0049] The modified microcapsules are prepared by the following steps: Step B1: Bromopropylene, acetonitrile and isonicotinic acid are mixed evenly and reacted at 110 r / min and 90℃ for 8 h to obtain intermediate 3. Intermediate 3 and N-hydroxysuccinimide are mixed evenly and stirred at 120 r / min and 30℃. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water are added and reacted for 2 h. Then, an acetic acid solution of chitosan is added and reacted for 24 h to obtain quaternized chitosan. Step B2: Mix copper sulfate pentahydrate, deionized water, and ammonia water evenly, and react for 30 minutes at 130 r / min and 30°C. Stir and add quaternized chitosan, and react for 2 hours. Raise the temperature to 75°C, add sodium sulfide nonahydrate, and react for 50 minutes to obtain the modified wall material. Mix cinnamon essential oil, Tween 80, and deionized water evenly, and shear at high speed for 15 minutes at 7000 r / min and 30°C to obtain cinnamon flavor emulsion. Mix the cinnamon flavor emulsion and gum arabic aqueous solution evenly, and stir for 50 minutes at 6000 r / min to obtain single-capsule wall cinnamon flavor microcapsule emulsion. Step B3: Mix lavender essential oil, Tween 80, and deionized water evenly, and shear at high speed for 15 minutes at 7000 r / min and 30℃ to obtain lavender fragrance emulsion. Mix the lavender fragrance emulsion and gum arabic aqueous solution evenly, and stir at 6000 r / min for 50 minutes to obtain single-cell wall lavender microcapsule emulsion. Mix the single-cell wall cinnamon microcapsule emulsion and the single-cell wall lavender microcapsule emulsion evenly, stir at 130 r / min, and add modified wall material aqueous solution to obtain modified microcapsules.

[0050] In step B1, the molar ratio of bromopropene and isonicotinic acid is 1.1:1. The volume ratio of intermediate 3, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, deionized water, and acetic acid solution of chitosan is 5 mmol:4.2 mmol:4.2 mmol:20 mL:50 mL. The acetic acid solution of chitosan is prepared by adding 2 mmol of chitosan to 50 mL of 2% acetic acid solution.

[0051] In step B2, the ratio of copper sulfate pentahydrate, deionized water, ammonia, quaternized chitosan, and sodium sulfide nonahydrate is 0.1g:30mL:4mL:0.1g:0.2g, the molar concentration of ammonia is 7mol / L, the ratio of cinnamon essential oil, Tween 80, and deionized water is 1g:1g:8mL, the ratio of cinnamon flavor emulsion and gum arabic aqueous solution is 1mL:1.5mL, and the mass fraction of gum arabic aqueous solution is 1%.

[0052] In step B3, the ratio of lavender essential oil, Tween 80, and deionized water is 1g:1g:8mL; the ratio of lavender fragrance emulsion to gum arabic aqueous solution is 1mL:1.5mL; the mass fraction of gum arabic aqueous solution is 1%; and the ratio of single-cell wall cinnamon microcapsule emulsion, single-cell wall lavender microcapsule emulsion, and modified wall material aqueous solution is 1mL:1mL:2mL; the mass fraction of modified wall material aqueous solution is 1%.

[0053] Comparative Example 1: Compared with Example 1, no intermediate 1 was added in step A2 of this comparative example, but the other steps were the same.

[0054] Comparative Example 2: This comparative example uses quaternized chitosan instead of the modified wall material compared to Example 1, while the other steps are the same.

[0055] Comparative Example 3: This comparative example uses a single-walled cinnamon microcapsule emulsion instead of modified microcapsules, compared to Example 1, with the other steps remaining the same.

[0056] The antibacterial rate of the acetate fiber fabrics containing natural fragrances prepared in Examples 1-3 and Comparative Examples 1-3 was tested according to GB / T20944.2-2007 standard, and the test results are shown in Table 1. The fabrics were cut, and 0.4g was weighed as a sample. The sample was pre-treated for sterilization using an autoclave, and Staphylococcus aureus and Escherichia coli were selected as test bacteria.

[0057] The aroma of the acetate fiber fabrics containing natural fragrances prepared in Examples 1-3 and Comparative Examples 1-3 was tested using a portable odor sensor. The results are shown in Table 1. The portable odor sensor can measure low concentrations of odors or odor molecules, displaying subtle changes and intensities that are difficult for the human sense of smell to detect, with values ​​ranging from 000 to 999. The fabrics were washed once and dried three times, and the aroma value was measured after 10 washes.

[0058] Table 1

[0059] Table 1 shows that the acetate fiber fabrics containing natural fragrance prepared in Examples 1-3 exhibited antibacterial rates of 99.90-99.97% against Staphylococcus aureus and 99.91-99.96% against Escherichia coli, both exceeding 99.9%. After 10 washes, the odor values ​​detected by a portable odor sensor were in the range of 71-75. This indicates that the present invention has excellent antibacterial effect and long-lasting fragrance.

[0060] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A production process for acetate fiber fabric containing natural fragrance, characterized in that: Specifically, it includes the following steps: Step S1: Mix the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules and dimethylformamide evenly to make a spinning solution, dry spin, and then irradiate with ultraviolet light to obtain pretreated fibers, which are then knitted to obtain pretreated fabric. Step S2: Place the pretreated fabric in a sodium hypochlorite solution, adjust the pH of the solution, soak and wash, and then dry to obtain an acetate fiber fabric with natural fragrance. The weight ratio of the modified polymer, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, modified microcapsules and dimethylformamide in step S1 is 70-80:0.3-0.6:6-8:100-120; The modified polymer is prepared by the following steps: Step A1: Mix 5,5-dimethylhydantoin, ethanol and sodium hydroxide and stir, then add 3-chloro-1,2-propanediol and react to obtain intermediate 1. Mix 3-mercapto-1,2-propanediol, acetonitrile and tert-butyl disulfide and stir, then add triethylamine and react to obtain intermediate 2. Step A2: Mix hexamethylene diisocyanate, dimethylformamide, dibutyltin disilicate, intermediate 1 and intermediate 2 evenly, react them, stir and add cellulose acetate and triethylamine, react them to obtain the pretreated polymer; Step A3: Mix and stir the pretreated polymer, tetrahydrofuran and deionized water, add tris(2-carboxyethyl)phosphine hydrochloride, and react to obtain the modified polymer; The modified microcapsules are prepared by the following steps: Step B1: Mix bromopropylene, acetonitrile and isonicotinic acid evenly and react to obtain intermediate 3. Mix intermediate 3 and N-hydroxysuccinimide and stir, then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water and react. Add acetic acid solution of chitosan and react to obtain quaternized chitosan. Step B2: Mix copper sulfate pentahydrate, deionized water and ammonia water evenly, react, stir and add quaternized chitosan, react, heat, add sodium sulfide nonahydrate, react to obtain modified wall material, mix cinnamon essential oil, Tween 80 and deionized water evenly, and shear at high speed to obtain cinnamon flavor emulsion, mix cinnamon flavor emulsion and gum arabic aqueous solution evenly, stir to obtain single-capsule wall cinnamon flavor microcapsule emulsion; Step B3: Mix lavender essential oil, Tween 80 and deionized water evenly, and shear at high speed to obtain lavender fragrance emulsion. Mix the lavender fragrance emulsion and gum arabic aqueous solution evenly and stir to obtain single-cell wall lavender microcapsule emulsion. Mix the single-cell wall cinnamon microcapsule emulsion and the single-cell wall lavender microcapsule emulsion evenly, stir and add modified wall material aqueous solution to obtain modified microcapsules.

2. The production process of acetate fiber fabric containing natural fragrance according to claim 1, characterized in that: In step A1, the ratio of 5,5-dimethylhydantoin, sodium hydroxide, and 3-chloro-1,2-propanediol is 1 mmol:1 mmol:1.1 mmol, and the ratio of 3-mercapto-1,2-propanediol, tert-butyl disulfide, and triethylamine is 1 mmol:1.2 mmol:1.1 mmol.

3. The production process of acetate fiber fabric containing natural fragrance according to claim 1, characterized in that: In step A2, the ratio of hexamethylene diisocyanate, intermediate 1, intermediate 2, and cellulose acetate is 1 mol: 0.2-0.3 mol: 0.2-0.3 mol: 0.8-1 mol, the amount of dibutyltin disilicate is 0.05-0.1% of the mass of hexamethylene diisocyanate, and the amount of triethylamine is 0.1-0.3% of the mass of hexamethylene diisocyanate.

4. The production process of acetate fiber fabric containing natural fragrance according to claim 1, characterized in that: The molar ratio of disulfide bonds and tris(2-carboxyethyl)phosphine hydrochloride on the pretreated polymer in step A3 is 1:1.5-2.

5. The production process of acetate fiber fabric containing natural fragrance according to claim 1, characterized in that: In step B1, the molar ratio of bromopropylene and isonicotinic acid is 1.1:1, and the volume ratio of intermediate 3, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, deionized water and acetic acid solution of chitosan is 5 mmol:4.2 mmol:4.2 mmol:20 mL:50 mL.

6. The production process of acetate fiber fabric containing natural fragrance according to claim 1, characterized in that: In step B2, the ratio of copper sulfate pentahydrate, deionized water, ammonia, quaternized chitosan, and sodium sulfide nonahydrate is 0.1g:30mL:4mL:0.1g:0.2g; the ratio of cinnamon essential oil, Tween 80, and deionized water is 1g:0.5-1g:6-8mL; and the ratio of cinnamon flavor emulsion and gum arabic aqueous solution is 1mL:1.5mL.

7. The production process of acetate fiber fabric containing natural fragrance according to claim 1, characterized in that: In step B3, the ratio of lavender essential oil, Tween 80, and deionized water is 1g:0.5-1g:6-8mL; the ratio of lavender fragrance emulsion and gum arabic aqueous solution is 1mL:1.5mL; and the ratio of single-cell wall cinnamon microcapsule emulsion, single-cell wall lavender microcapsule emulsion, and modified wall material aqueous solution is 1mL:1mL:1.5-2mL.

Images