A viscose macrofiber containing antioxidant active ingredients and its preparation method

Abstract

This invention provides a viscose macro-biofiber containing antioxidant active ingredients and its preparation method, comprising the following raw materials by weight: 1000 parts spinning solution, 9-11 parts molecular nest, 5-10 parts γ-glycidyl etheroxypropyltrimethoxysilane, 6-8 parts sodium alginate, 4-6 parts sodium carboxymethyl cellulose, and 140-150 parts water. This invention proposes a viscose macro-biofiber containing antioxidant active ingredients, improving the stability of the free radical scavenging active ingredients in the fiber under high temperature and light conditions, and mitigating the problem of significant decrease in the fiber's free radical scavenging performance due to the decomposition of active ingredients; it also improves the persistence of the free radical scavenging active ingredients during fiber use, mitigating the problem of reduced fiber lifespan and functional effects due to the loss of active ingredients.

Description

Technical Field

[0001] This invention relates to the field of fiber manufacturing technology, specifically to a viscose macro-biofiber containing antioxidant active ingredients and its preparation method. Background Technology

[0002] Clothing made from viscose macrocellulose containing antioxidant active ingredients can come into direct contact with human skin, continuously releasing antioxidants to effectively remove free radicals from the skin's surface and reduce damage to the skin from factors such as ultraviolet rays and environmental pollution, thus playing a role in skin care, beauty, and delaying skin aging. At the same time, this fiber has good moisture absorption and breathability, making it comfortable to wear and suitable for making various kinds of underwear.

[0003] In the field of fiber materials, various active ingredients are often introduced to endow fibers with more functionality. Many components with free radical scavenging activity, such as flavonoids and polyphenols, face numerous problems in fiber preparation and application. On the one hand, these active ingredients are chemically unstable and decompose rapidly under high temperature and light conditions. For example, high-temperature treatment is a common process in fiber processing, while light exposure occurs throughout the production, storage, and transportation stages. This leads to a significant reduction in the content of free radical scavenging active ingredients in the fiber, resulting in a significant decrease in the fiber's free radical scavenging performance and rendering it unable to effectively perform its function. On the other hand, during fiber use, the free radical scavenging active ingredients are gradually lost due to continuous contact with the external environment. For example, during daily washing, friction, and interaction with oxygen and moisture in the air, active ingredients are continuously lost. This not only affects the fiber's lifespan but also reduces its functional effectiveness, making it difficult to meet the requirements of practical applications for fiber performance stability and durability.

[0004] Furthermore, the physical and chemical properties of viscose macrofibers may change after the introduction of free radical scavenging active ingredients. In terms of physical properties, the addition of active ingredients may affect the spinning performance of the fiber. Spinning is a crucial step in fiber preparation; the presence of active ingredients may lead to problems such as fiber breakage and fuzzing during spinning, reducing fiber strength and uniformity, and affecting fiber quality and subsequent processing performance. In terms of chemical properties, the interaction between the active ingredients and the fiber matrix may affect the fiber's dyeing properties, moisture absorption, and air permeability. For example, active ingredients may affect the internal pore structure of the fiber, reducing its moisture absorption and air permeability, thus lowering the overall performance of the fiber and failing to meet the multifaceted performance requirements of practical applications. Based on this, the present invention provides a viscose macrofiber containing antioxidant active ingredients and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to provide a viscose macro-biofiber containing antioxidant active ingredients and its preparation method, which improves the stability of the free radical scavenging active ingredients in the fiber under high temperature and light conditions, and improves the problem of significant decline in the fiber's free radical scavenging performance due to the decomposition of active ingredients; improves the durability of the free radical scavenging active ingredients during fiber use, and improves the problem of reduced fiber lifespan and functional effects due to loss of active ingredients; improves the spinning performance of viscose macro-biofiber after the introduction of antioxidant active ingredients, reduces problems such as breakage and fuzzing, and improves fiber strength and uniformity; and improves the overall performance of viscose macro-biofiber containing antioxidant active ingredients, avoiding the decrease in moisture absorption and breathability caused by the interaction between antioxidant ingredients and the fiber matrix.

[0006] On one hand, the present invention provides a viscose macro-fiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts of spinning solution, 9-11 parts of molecular nest, 5-10 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 6-8 parts of sodium alginate, 4-6 parts of sodium carboxymethyl cellulose, and 140-150 parts of water.

[0007] Further, the method for preparing the molecular nest includes: ultrasonically dispersing naringenin and tea polyphenols in anhydrous ethanol to obtain an antioxidant mixed solution; immersing halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane in the antioxidant mixed solution, immersing at -0.095±0.005MPa and 35-45℃ for 3-4h, filtering under normal pressure, collecting the solid, and drying to obtain the final product.

[0008] In this invention, molecular nests have a synergistic effect in improving the loading of antioxidant components and the overall performance of fibers. Structurally, the molecular nests possess a unique hollow tubular structure, which provides a large specific surface area and internal space for serving as carriers of antioxidants. The large specific surface area allows more antioxidant molecules to adsorb onto the surface of the molecular nest, while the internal space can further accommodate antioxidant molecules, thereby increasing the antioxidant loading capacity. Simultaneously, the hollow tubular structure can protect the loaded antioxidant molecules to a certain extent, reducing the direct effects of external environments (such as high temperature and oxygen) on the antioxidants, thus contributing to improved stability of the antioxidants during preparation and storage. During fiber preparation, halloysite nanotubes loaded with antioxidants are uniformly dispersed in the fiber matrix. Their nanoscale structure can act as a reinforcing phase, generating good interfacial interactions with the fiber matrix. This interaction can effectively transfer stress, improving the strength and uniformity of the fibers. Moreover, the hollow structure of halloysite nanotubes does not clog the pores inside the fiber like some solid particles, thus avoiding the problem of decreased moisture absorption and breathability caused by the interaction between antioxidant components and the fiber matrix. This is beneficial to improving the overall performance of viscose macrofiber containing antioxidant active ingredients.

[0009] This invention selects naringenin and tea polyphenols as antioxidants. The choice of these two antioxidants has a synergistic effect on improving the antioxidant and overall performance of the fiber. From the perspective of antioxidant mechanism, both naringenin and tea polyphenols have multiple phenolic hydroxyl structures. These phenolic hydroxyl groups can provide active hydrogen atoms to react with free radicals, thereby interrupting the chain reaction of free radicals and achieving the purpose of antioxidation. Moreover, there is a synergistic effect between the two in the antioxidant process. Naringenin and tea polyphenols can complement each other, capturing free radicals from different pathways and mechanisms, more comprehensively clearing free radicals in the fiber, and improving the fiber's antioxidant capacity. During fiber preparation and storage, this strong antioxidant capacity can effectively prevent the fiber's performance degradation due to oxidation, such as reduced strength, thereby ensuring the fiber's quality and stability. Simultaneously, because naringenin and tea polyphenols can be stably loaded on molecular nests and uniformly distributed in the fiber through interaction with the fiber matrix, they will not negatively affect other fiber properties. On the contrary, their good compatibility with the fiber matrix helps improve the internal structure of the fiber, reduce problems such as stress concentration that may be caused by the introduction of antioxidants, and thus improve the spinning performance and overall performance of the fiber, avoiding the decline in moisture absorption and breathability caused by the interaction between antioxidants and the fiber matrix.

[0010] Furthermore, the ratio of naringenin, tea polyphenols, anhydrous ethanol, and halloysite nanotubes modified with silane coupling agent is 10-12g:10-12g:480-520mL:100g.

[0011] Further, the silanization modification step includes: dispersing the dried halloysite nanotubes in a mixed solution of ethanol and water, sonicating them at 250-300W for 30-40 min, adding γ-aminopropyltriethoxysilane and reacting at 55-65℃ and 550-650rpm for 5-6 h, and then centrifuging, washing and drying to obtain the final product.

[0012] This invention selects γ-aminopropyltriethoxysilane as a silane coupling agent, a choice that has a synergistic effect on improving the stability of antioxidant components and enhancing fiber properties. Upon hydrolysis, γ-aminopropyltriethoxysilane generates silanol groups, which can undergo dehydration condensation with the hydroxyl groups on the halloysite nanotube surface, thereby chemically bonding γ-aminopropyltriethoxysilane to the halloysite nanotube surface. This process not only modifies the halloysite nanotube surface by introducing amino groups but also alters its surface properties, changing it from hydrophilic to somewhat lipophilic. When subsequently loading antioxidants (naringenin and tea polyphenols), the carboxyl groups and other groups in the antioxidant molecules can form hydrogen bonds and other interactions with the modified amino groups on the halloysite nanotube surface, enhancing the binding force between the antioxidant and the halloysite nanotube. This strong binding force effectively prevents antioxidants from detaching or degrading under the high-temperature environment during fiber preparation and the physical and chemical effects during storage, thereby improving the stability of antioxidant components in viscose macrofibers containing antioxidant active ingredients during preparation and storage. Simultaneously, because the antioxidants can be stably loaded onto halloysite nanotubes and uniformly distributed within the fiber, the fiber's structure and properties are not affected by the aggregation or detachment of antioxidants. This, in turn, helps improve the fiber's spinning performance, reduces problems such as breakage and fuzzing, and enhances fiber strength and uniformity.

[0013] Furthermore, the drying pretreatment step includes drying halloysite nanotubes at a temperature of 100-110℃ and a pressure of -0.1±0.05MPa for 4-5 hours.

[0014] Furthermore, the ratio of the dried halloysite nanotubes, ethanol, water and γ-aminopropyltriethoxysilane used is 100g:1000-1100mL:400-500mL:10-12g.

[0015] Furthermore, the halloysite nanotubes have an inner diameter of 15 nm and a length of 1-2 μm.

[0016] On the other hand, the present invention also provides a method for preparing viscose macrocellulose containing antioxidant active ingredients, the steps of which include: dispersing molecular nests in water, then adding γ-glycidyl etheroxypropyltrimethoxysilane, sodium alginate, sodium carboxymethyl cellulose, and a spinning solution containing 9.1-9.3 wt% methyl cellulose and 2.8-3.2 wt% total alkali, mixing at 40-50°C and 450-550 rpm for 2-3 hours, and filtering. The spinning solution with a viscosity of 45-47s is obtained by degassing at 35-45℃ for 2-3 hours and maturing at 18±1℃ for 40-48 hours. The spinning solution is then introduced into a spinning machine and spun at a spinning speed of 16-18m / min. The spinning solution is then held in a coagulation bath at 45±1℃ for 20-25 seconds. After solidification, the spun fibers are desulfurized, washed with water at 60-65℃, oiled, and heat-set to obtain viscose macro-fibers containing antioxidant active ingredients.

[0017] Furthermore, the content of each component in the coagulation bath is as follows: sulfuric acid 75-85 g / L, sodium sulfate 115-125 g / L, and ferric chloride 4-5 g / L.

[0018] Furthermore, the oiling rate is 1-1.2%, and the heat setting is achieved by hot air relaxation setting at 110-120℃ for 150±30s.

[0019] The beneficial effects of this invention are as follows:

[0020] This invention innovatively employs naringenin and tea polyphenols as antioxidants, loading these two antioxidants onto halloysite nanotubes after silanization modification with γ-aminopropyltriethoxysilane. From a synergistic perspective, naringenin and tea polyphenols exhibit synergistic antioxidant effects; their combination can more effectively capture free radicals, exert antioxidant functions, and enhance the antioxidant performance of the fiber. Furthermore, γ-aminopropyltriethoxysilane modification of halloysite nanotubes introduces amino groups into the molecular nest, enabling it to form hydrogen bonds with the antioxidants, strengthening the binding force between the molecular nest and the antioxidants, effectively preventing the antioxidants from detaching during fiber preparation and storage, and ensuring the stability of the antioxidant components. On the other hand, the pretreatment drying step eliminates moisture interference in the halloysite nanotubes, avoiding the hindrance of moisture to the silane modification reaction, improving loading efficiency, and further ensuring the stability and effectiveness of the loading system. The construction of this antioxidant-loaded system, from the selection of antioxidants and carrier modification to the loading process, involves synergistic cooperation among all stages, jointly improving the antioxidant performance and stability of the fiber. Detailed Implementation

[0021] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, 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. The raw materials used in the following embodiments are all commercially available.

[0022] Example 1

[0023] This embodiment provides a viscose bio-fiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts spinning solution, 10 parts molecular nest, 8 parts γ-glycidyl etheroxypropyltrimethoxysilane, 7 parts sodium alginate, 5 parts sodium carboxymethyl cellulose, and 1405 parts water.

[0024] The method for preparing this type of viscose macrocellulose containing antioxidant active ingredients includes the following steps:

[0025] Molecular nests with an inner diameter of 15 nm and an average length of 1.5 μm were dried at 105 °C and -0.1 MPa for 4.5 h. 100 g of the pre-dried halloysite nanotubes were dispersed in a mixed solution of 1050 mL ethanol and 450 mL water and sonicated at 280 W for 35 min. 11 g of γ-aminopropyltriethoxysilane was added and reacted at 60 °C and 600 rpm for 5.5 h. After centrifugation at 8000 rpm for 10 min, the precipitate was washed three times with anhydrous ethanol and dried under vacuum at 60 °C for 12 h to obtain alkylated halloysite nanotubes.

[0026] 11g of naringenin and 11g of tea polyphenols were ultrasonically dispersed in 500mL of anhydrous ethanol to obtain an antioxidant mixed solution. 100g of halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane were immersed in the antioxidant mixed solution and immersed at -0.095MPa and 40℃ for 3.5h. After filtration at normal pressure, the solid was collected and dried under vacuum at 60℃ for 6h to obtain molecular nests.

[0027] Molecular nests were dispersed in water, followed by the addition of γ-glycidyl etheroxypropyltrimethoxysilane, sodium alginate, sodium carboxymethyl cellulose, and a spinning solution containing 9.2 wt% methyl cellulose and 3 wt% total alkali. The mixture was stirred at 45°C and 500 rpm for 2.5 h, filtered, degassed at 40°C for 2.5 h, and matured at 18°C ​​for 44 h to obtain a spinning solution with a viscosity of 46 s. The spinning solution was introduced into a spinning machine and spun at a speed of 17 m / min. The spun fibers were then held in a coagulation bath at 45°C for 22 s. The components in the coagulation bath were: sulfuric acid 80 g / L, sodium sulfate 120 g / L, and ferric chloride 4.5 g / L. After spinning and solidification, the fibers were desulfurized, washed with water at 62°C, oiled at a controlled oiling rate of 1.1%, and then relaxed and set with hot air at 115°C for 150 s to obtain viscose macrofiber containing antioxidant active ingredients.

[0028] Example 2

[0029] This embodiment provides a viscose macro-fiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts spinning solution, 9 parts molecular nest, 5 parts γ-glycidyl etheroxypropyltrimethoxysilane, 6 parts sodium alginate, 4 parts sodium carboxymethyl cellulose, and 140 parts water.

[0030] The method for preparing this type of viscose macrocellulose containing antioxidant active ingredients includes the following steps:

[0031] Halloysite nanotubes with an inner diameter of 15 nm and an average length of 1.5 μm were dried at 100 °C and -0.1 MPa for 4 h. 100 g of the pre-dried halloysite nanotubes were dispersed in a mixed solution of 1000 mL ethanol and 400 mL water and sonicated at 250 W for 30 min. 10 g of γ-aminopropyltriethoxysilane was added and reacted at 55 °C and 550 rpm for 5 h. After centrifugation at 8000 rpm for 10 min, the precipitate was washed three times with anhydrous ethanol and dried under vacuum at 60 °C for 12 h to obtain alkylated halloysite nanotubes.

[0032] 10g of naringenin and 10g of tea polyphenols were ultrasonically dispersed in 480mL of anhydrous ethanol to obtain an antioxidant mixed solution. 100g of halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane were immersed in the antioxidant mixed solution and immersed at -0.095MPa and 35℃ for 3h. After filtration at normal pressure, the solid was collected and dried under vacuum at 60℃ for 6h to obtain molecular nests.

[0033] Molecular nests were dispersed in water, followed by the addition of γ-glycidyl etheroxypropyltrimethoxysilane, sodium alginate, sodium carboxymethyl cellulose, and a spinning solution containing 9.1 wt% methyl cellulose and 2.8 wt% total alkali. The mixture was stirred at 40°C and 450 rpm for 2 hours, filtered, degassed at 35°C for 2 hours, and matured at 18°C ​​for 40 hours to obtain a spinning solution with a viscosity of 45 s. The spinning solution was introduced into a spinning machine and spun at a speed of 16 m / min. The spun fibers were then held in a coagulation bath at 45°C for 20 seconds. The components in the coagulation bath were: sulfuric acid 75 g / L, sodium sulfate 115 g / L, and ferric chloride 4 g / L. After spinning and solidification, the fibers were desulfurized, washed with water at 60°C, oiled at a controlled oiling rate of 1%, and then relaxed and set with hot air at 110°C for 150 seconds to obtain viscose macrofiber containing antioxidant active ingredients.

[0034] Example 3

[0035] This embodiment provides a viscose bio-fiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts spinning solution, 11 parts molecular nest, 10 parts γ-glycidyl etheroxypropyltrimethoxysilane, 8 parts sodium alginate, 6 parts sodium carboxymethyl cellulose, and 150 parts water.

[0036] The method for preparing this type of viscose macrocellulose containing antioxidant active ingredients includes the following steps:

[0037] Halloysite nanotubes with an inner diameter of 15 nm and an average length of 1.5 μm were dried at 110 °C and -0.1 MPa for 5 h. 100 g of the pre-dried halloysite nanotubes were dispersed in a mixed solution of 1100 mL ethanol and 500 mL water and sonicated at 300 W for 40 min. 12 g of γ-aminopropyltriethoxysilane was added and reacted at 65 °C and 650 rpm for 6 h. After centrifugation at 8000 rpm for 10 min, the precipitate was washed three times with anhydrous ethanol and dried under vacuum at 60 °C for 12 h to obtain alkylated halloysite nanotubes.

[0038] 12g of naringenin and 12g of tea polyphenols were ultrasonically dispersed in 520mL of anhydrous ethanol to obtain an antioxidant mixed solution. 100g of halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane were immersed in the antioxidant mixed solution and immersed at -0.095MPa and 45℃ for 4h. After filtration at normal pressure, the solid was collected and dried under vacuum at 60℃ for 6h to obtain molecular nests.

[0039] Molecular nests were dispersed in water, followed by the addition of γ-glycidyl etheroxypropyltrimethoxysilane, sodium alginate, sodium carboxymethyl cellulose, and a spinning solution containing 9.3 wt% methyl cellulose and 3.2 wt% total alkali. The mixture was stirred at 50°C and 550 rpm for 3 hours, filtered, degassed at 45°C for 3 hours, and matured at 18°C ​​for 48 hours to obtain a spinning solution with a viscosity of 47 s. The spinning solution was introduced into a spinning machine and spun at a speed of 18 m / min. The spun fibers were then held in a coagulation bath at 45°C for 25 seconds. The components in the coagulation bath were: sulfuric acid 85 g / L, sodium sulfate 125 g / L, and ferric chloride 5 g / L. After spinning and solidification, the fibers were desulfurized, washed with water at 65°C, oiled at a controlled oiling rate of 1.2%, and then relaxed and set with hot air at 120°C for 150 seconds to obtain viscose macro-fibers containing antioxidant active ingredients.

[0040] Comparative Example 1

[0041] Based on Example 1, adjustments were made, except that halloysite nanotubes were replaced with multi-walled carbon nanotubes of equal mass, with an average inner diameter of 15 nm and an average length of 1.5 μm.

[0042] Comparative Example 2

[0043] The method is based on Example 1, but with the difference that halloysite nanotubes are replaced with mesoporous silica (SBA-15) of equal mass.

[0044] Comparative Example 3

[0045] The method is based on Example 1, but with the difference that γ-aminopropyltriethoxysilane is replaced with an equimolar mass of silane coupling agent KH570.

[0046] Comparative Example 4

[0047] The method was modified based on Example 1, except that the halloysite nanotubes were not dried during the preparation of the molecular nests.

[0048] Comparative Example 5

[0049] Based on Example 1, adjustments were made. Unlike Example 1, the molecular nests were prepared by silane modification, and the dried pretreated halloysite nanotubes were directly impregnated and loaded with antioxidants. The preparation conditions were the same as in Example 1.

[0050] Comparative Example 6

[0051] The method was modified based on Example 1, except that the naringenin in the antioxidant mixture was replaced with an equal mass of tea polyphenols.

[0052] Comparative Example 7

[0053] The method was modified based on Example 1, except that the tea polyphenols in the antioxidant mixture were replaced with an equal mass of naringenin.

[0054] Comparative Example 8

[0055] The method is an adjustment based on Example 1, except that the molecular nests are replaced with halloysite nanotubes.

[0056] Experimental Example: The properties of the viscose macrofibers prepared in Examples 1-3 and Comparative Examples 1-8 were investigated, and the following tests were conducted:

[0057] Mechanical property testing: The test method shall be in accordance with GB / T 14344-2022 "Test method for tensile properties of chemical fiber filaments" and the test shall be no less than 30 filaments, and the average value of the test shall be taken.

[0058] Hygroscopicity: Referring to GB / T 9995-1997 "Determination of Moisture Content and Moisture Regain of Textile Materials by Oven Method", the dried fiber sample (Wd) was equilibrated for 24 hours under standard atmospheric conditions (20℃±2℃, 65%±4% RH), and the weight after moisture absorption (Wm) was weighed. Moisture regain (%) = (Wm-Wd) / Wd*100%;

[0059] Air permeability test: The air permeability rate was tested in accordance with GB / T 5453-2025 "Textiles - Determination of Air Permeability of Fabrics";

[0060] Free radical scavenging rate: Detected according to the DPPH free radical scavenging rate detection method and ABTS. + • The free radical scavenging rate was tested using a detection method;

[0061] Antibacterial performance test: According to the method in GB / T20944.3-2008, the inhibition rate of each viscose macrocellulose containing antioxidant active ingredients against Staphylococcus aureus (ATCC6538), Escherichia coli (ATCC8739), and Candida albicans (ATCC10231) was tested, and the inhibition rate after 100 washes was also tested.

[0062] The test results are shown in Tables 1 and 2 below:

[0063] Table 1

[0064]

[0065] Table 2

[0066]

[0067]

[0068] Based on the foregoing, Examples 1-3 exhibit stable mechanical properties, with superior dry fracture strength and hygroscopicity compared to the comparative examples. The initial antibacterial rate of the three bacterial strains was >92%, dependent on the synergistic antioxidant effect of naringenin and tea polyphenols; the antibacterial rate remained >85% after 100 washes and aging, demonstrating the high stability of the halloysite nanotube loading system. γ-aminopropyltriethoxysilane modification enhanced the binding force between halloysite and antioxidants; pretreatment drying eliminated moisture interference and improved loading efficiency. Comparative Example 1: The smooth surface of carbon nanotubes resulted in low antioxidant loading and easy detachment. Due to the inability to effectively load / release antioxidants, the free radical scavenging rate approached 0. Comparative Example 2: Mesoporous silica with a single pore size resulted in poor antioxidant slow-release effect and decreased mechanical strength. Comparative Example 3: KH570 lacked amino groups, making it unable to form hydrogen bonds with antioxidants, leading to weak binding and easy loss. Comparative Example 4: Without drying pretreatment, residual moisture hindered the silane modification reaction, resulting in uneven loading. Comparative Example 5: Direct loading without silane modification resulted in weak hydrophilicity of halloysite surface, reducing antioxidant adsorption by more than 60%. Comparative Example 6: Lacking the synergistic effect of phenolic hydroxyl groups of naringenin, the antibacterial rate against Gram-positive bacteria decreased by more than 10%, and the DPPH· free radical / ABTS ratio was high. + • Free radical scavenging rate decreased slightly; Comparative Example 7 showed poor thermal stability of naringenin, resulting in a significant decrease in scavenging rate, and the release efficiency decreased due to the lipid solubility of naringenin; Comparative Example 8 was not loaded with antioxidants, had no active ingredients, and its antibacterial performance was close to blank.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention; those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention; and all technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A viscose macrobiological fibre containing an antioxidant active ingredient, characterised in that, It comprises the following raw materials by weight: 1000 parts of spinning dope, 9-11 parts of molecular nest, 5-10 parts of gamma-glycidoxypropyltrimethoxysilane, 6-8 parts of sodium alginate, 4-6 parts of sodium carboxymethyl cellulose, and 140-150 parts of water; The preparation method of the molecular nest comprises: ultrasonic dispersion of naringin and tea polyphenol in anhydrous ethanol to obtain an antioxidant mixed solution; impregnation of halloysite nanotubes modified by silanization with gamma-aminopropyl triethoxysilane in the antioxidant mixed solution, impregnation at-0.095±0.005MPa and 35-45℃ for 3-4h, normal pressure filtration, collection of the solid, and drying to obtain the molecular nest. The silanization modification step comprises: dispersing the halloysite nanotubes after drying pretreatment in a mixed solution of ethanol and water, ultrasonic treatment at 250-300W for 30-40min, addition of gamma-aminopropyl triethoxysilane, reaction at 55-65℃ and 550-650rpm for 5-6h, centrifugation, washing, and drying to obtain the halloysite nanotubes; the drying pretreatment step comprises: drying the halloysite nanotubes at a temperature of 100-110℃ and-0.1±0.05MPa for 4-5h.

2. The antioxidant active ingredient-containing biofibers according to claim 1, wherein The dosage ratio of the naringin, tea polyphenol, anhydrous ethanol, and halloysite nanotubes modified by a silane coupling agent is 10-12g:10-12g:480-520mL:100g.

3. The antioxidant active ingredient-containing viscose macrobiological fiber according to claim 1, characterized in that, The dosage ratio of the halloysite nanotubes after drying pretreatment, ethanol, water, and gamma-aminopropyl triethoxysilane is 100g:1000-1100mL:400-500mL:10-12g.

4. The antioxidant active ingredient-containing biofibers according to claim 1, wherein The halloysite nanotubes have an inner diameter of 15nm and a length of 1-2μm.

5. A process for the preparation of antioxidant active ingredient containing viscose macrobiological fibre as claimed in any one of claims 1-4, characterized by the steps of It comprises: The molecular nest is dispersed in water, and then gamma-glycidoxypropyltrimethoxysilane, sodium alginate, and sodium carboxymethyl cellulose are added, and a spinning dope containing 9.1-9.3wt% of methyl cellulose and 2.8-3.2wt% of total alkali is mixed at 40-50℃ and 450-550rpm for 2-3h, and then filtration, degassing at 35-45℃ for 2-3h, aging at 18±1℃ for 40-48h are performed to obtain a spinning solution with a viscosity of 45-47s, the spinning solution is introduced into a spinning machine, spinning treatment is performed at a spinning speed of 16-18m / min, the spinning is stopped in a coagulation bath with a temperature of 45±1℃ for 20-25s, and then desulfurization, water washing at 60-65℃, oiling, and heat setting are performed to obtain the antioxidant active ingredient-containing viscose large biological fiber.

6. The process for the preparation of antioxidant active ingredient containing viscose macro-biological fiber according to claim 5, characterized in that, The content of each component in the coagulation bath is: 75-85g / L of sulfuric acid, 115-125g / L of sodium sulfate, and 4-5g / L of ferric chloride.

7. The process for the preparation of antioxidant active ingredient containing viscose macro-biological fiber according to claim 5, characterized in that, The oiling rate of the oiling is 1-1.2%, and the heat setting is 110-120℃ hot air relaxation setting with a setting time of 150±30s.

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