Viscose large bio-fiber containing antioxidant active component and preparation method of viscose large bio-fiber

Abstract

The invention provides viscose large biological fibers containing antioxidant active components and a preparation method of the viscose large biological fibers. The viscose large biological fibers are prepared from the following raw materials in parts by weight: 1000 parts of spinning solution, 9-11 parts of molecular nests, 5-10 parts of gamma-glycidyl ether oxypropyl trimethoxy silane, 6-8 parts of sodium alginate, 4-6 parts of sodium carboxymethyl cellulose and 140-150 parts of water. According to the viscose large biological fiber containing the antioxidant active component, the stability of the free radical scavenging active component in the fiber under the conditions of high temperature and illumination is improved, and the problem that the free radical scavenging performance of the fiber is remarkably reduced due to decomposition of the active component is solved; the durability of scavenging free radical active ingredients in the fiber using process is improved, and the problems that the service life of the fiber is shortened and the functional effect is reduced due to loss of the active ingredients are solved.

Description

Technical Field

[0001] The invention relates to the technical field of fiber manufacturing, in particular to a viscose large biological fiber containing antioxidant active ingredients and a preparation method thereof. Background Art

[0002] Clothing made from viscose biofiber, which contains antioxidant active ingredients, can directly contact human skin, continuously releasing antioxidants to effectively scavenge free radicals on the skin's surface, reducing damage from UV rays, environmental pollution, and other factors, thereby protecting skin, beautifying it, and delaying skin aging. Furthermore, this fiber has excellent moisture absorption and breathability, making it comfortable to wear and suitable for various types of intimate apparel.

[0003] In the field of fiber materials, various active ingredients are often introduced to impart greater functionality to fibers. Many ingredients with free radical scavenging activity, such as flavonoids and polyphenolic compounds, face numerous challenges during fiber preparation and application. For one thing, these active ingredients are chemically unstable and rapidly decompose under high temperatures and light exposure. For example, high-temperature treatment is a common process in fiber processing, while light exposure occurs throughout the production, storage, and transportation stages. This can significantly reduce the content of these active ingredients in the fiber, significantly diminishing its free radical scavenging performance and rendering it ineffective. Furthermore, during fiber use, these active ingredients are gradually lost due to constant contact with the external environment. For example, through daily washing, friction, and interaction with oxygen and moisture in the air, these active ingredients are continuously lost. This not only shortens the fiber's lifespan but also reduces its functional effectiveness, making it difficult to meet the requirements for stable and durable fiber performance in practical applications.

[0004] In addition, after the introduction of free radical scavenging active ingredients, the physical and chemical properties of the viscose biofiber may change. In terms of physical properties, the addition of active ingredients may affect the spinning performance of the fiber. Spinning is a key link in fiber preparation. The presence of active ingredients may cause problems such as broken ends and hairy fibers during the spinning process, reduce the strength and uniformity of the fiber, and affect the quality of the fiber and subsequent processing performance. In terms of chemical properties, the interaction between the active ingredients and the fiber matrix may affect the dyeing properties, hygroscopicity and air permeability of the fiber. For example, the active ingredients may affect the internal pore structure of the fiber, reduce its hygroscopicity and air permeability, and reduce the comprehensive performance of the fiber, which cannot meet the requirements for various aspects of fiber performance in practical applications. Based on this, the present invention provides a viscose biofiber containing antioxidant active ingredients and a preparation method thereof. Summary of the Invention

[0005] The purpose of the present invention is to provide a viscose large biofiber containing antioxidant active ingredients and a preparation method thereof, which improves the stability of the free radical scavenging active ingredients in the fiber under high temperature and light conditions, and improves the problem that the fiber's free radical scavenging performance is significantly reduced due to the decomposition of the active ingredients; improves the durability of the free radical scavenging active ingredients during the use of the fiber, and improves the problem that the service life and functional effect of the fiber are reduced due to the loss of active ingredients; improves the spinning performance of the viscose large biofiber after the introduction of antioxidant active ingredients, reduces problems such as broken ends and hairy fibers, and improves the fiber strength and uniformity; improves the comprehensive performance of the viscose large biofiber containing antioxidant active ingredients, and avoids the decrease in moisture absorption and air permeability due to the interaction between the antioxidant ingredients and the fiber matrix.

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

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

[0008] The molecular nests of the present invention have a synergistic effect in terms of antioxidant loading and improvement of the overall performance of the fiber. From the perspective of structural characteristics, the molecular nests have a unique hollow tubular structure, which provides a larger specific surface area and internal space for it as a carrier of antioxidants. The larger specific surface area allows more antioxidant molecules to be adsorbed on the surface of the molecular nests, while the internal space can further accommodate antioxidant molecules, thereby increasing the loading amount of the antioxidant. At the same time, the hollow tubular structure can protect the loaded antioxidant molecules to a certain extent, reduce the direct effect of the external environment (such as high temperature, oxygen, etc.) on the antioxidants, and help to improve the stability of the antioxidants during preparation and storage. During the fiber preparation process, the halloysite nanotubes loaded with antioxidants are evenly dispersed in the fiber matrix, and their nanoscale structure can serve as a reinforcing phase to produce good interface interaction with the fiber matrix. This interaction can effectively transfer stress and improve the strength and uniformity of the fiber. Moreover, the hollow structure of halloysite nanotubes will not block the pores inside the fiber like some solid particles, thus avoiding the problem of decreased moisture absorption and air permeability due to the interaction between antioxidant components and the fiber matrix, which is beneficial to improving the comprehensive performance of viscose biofibers containing antioxidant active ingredients.

[0009] The present invention selects naringenin and tea polyphenols as antioxidants. The selection of these two antioxidants has a synergistic effect on improving the antioxidant properties and overall performance of the fiber. From the perspective of antioxidant mechanism, naringenin and tea polyphenols both have multiple phenolic hydroxyl structures, which can provide active hydrogen atoms to react with free radicals, thereby interrupting the free radical chain reaction and achieving the purpose of antioxidant. Moreover, the two have a synergistic effect in the antioxidant process. Naringenin and tea polyphenols can complement each other, capturing free radicals through different pathways and mechanisms, more comprehensively removing free radicals from the fiber, and improving the antioxidant capacity of the fiber. During the fiber preparation and storage process, this powerful antioxidant capacity can effectively prevent the performance degradation of the fiber caused by oxidation, such as reduced strength, thereby ensuring the quality and stability of the fiber. At the same time, because naringenin and tea polyphenols can be stably loaded on the molecular nest and evenly distributed in the fiber through interaction with the fiber matrix, they will not have a negative impact on other properties of the fiber. On the contrary, their good compatibility with the fiber matrix helps to improve the internal structure of the fiber, reduce stress concentration and other problems that may be caused by the introduction of antioxidant ingredients, thereby improving the spinning performance and comprehensive performance of the fiber, and avoiding the decrease in moisture absorption and air permeability due to the interaction between antioxidant ingredients and the fiber matrix.

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

[0011] Furthermore, the silanization modification step includes: dispersing the halloysite nanotubes after drying pretreatment in a mixed solution of ethanol and water, ultrasonically treating at 250-300W for 30-40min, adding γ-aminopropyltriethoxysilane and reacting at 55-65°C and 550-650rpm for 5-6h, centrifuging, washing and drying to obtain the product.

[0012] The present invention selects γ-aminopropyl triethoxysilane as a silane coupling agent, and this selection has a synergistic effect for improving the stability of antioxidant components and improving fiber performance. After hydrolysis, γ-aminopropyl triethoxysilane will produce a silanol group, which can undergo a dehydration condensation reaction with the hydroxyl group on the surface of the halloysite nanotube, thereby chemically bonding γ-aminopropyl triethoxysilane to the surface of the halloysite nanotube. This process not only modifies the surface of the halloysite nanotube, introduces an amino group, but also changes the surface properties of the halloysite nanotube, making it change from hydrophilic to having a certain lipophilicity. When the subsequent loading antioxidant (naringenin and tea polyphenols), the groups such as the carboxyl group in the antioxidant molecule can interact with the amino group after the surface modification of the halloysite nanotube to form hydrogen bonds, thereby enhancing the binding force between the antioxidant and the halloysite nanotube. This strong binding force effectively prevents the antioxidant from shedding or degrading due to the high temperatures encountered during fiber preparation and the physical and chemical effects of storage, thereby enhancing the stability of the antioxidant content in the viscose biofiber containing antioxidant active ingredients during preparation and storage. Furthermore, because the antioxidant is stably loaded onto the halloysite nanotubes and evenly distributed throughout the fiber, the fiber's structure and properties are not affected by antioxidant aggregation or shedding. This, in turn, improves the fiber's spinning performance, reduces problems such as broken ends and lint, and enhances fiber strength and uniformity.

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

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

[0015] Furthermore, the inner diameter of the halloysite nanotube is 15 nm and the length is 1-2 μm.

[0016] On the other hand, the present invention also provides a method for preparing a viscose biofiber containing antioxidant active ingredients, comprising the steps of: dispersing the molecular nest in water, then adding γ-glycidyloxypropyltrimethoxysilane, sodium alginate and sodium carboxymethyl cellulose and a spinning solution containing 9.1-9.3wt% of methyl cellulose and 2.8-3.2wt% of total alkali, mixing at 40-50°C and 450-550rpm for 2-3h, filtering, The spinning solution is degassed at 35-45°C for 2-3 hours and matured at 18±1°C for 40-48 hours to obtain a spinning solution with a viscosity of 45-47 seconds. The spinning solution is introduced into a spinning machine and spun at a spinning speed of 16-18 m / min. The spinning solution is placed in a coagulation bath at a temperature of 45±1°C for 20-25 seconds. After spinning and solidification, the solution is desulfurized, washed with water at 60-65°C, oiled, and heat-set to obtain a viscose biofiber containing antioxidant active ingredients.

[0017] Furthermore, the contents of the components in the coagulation bath are: 75-85 g / L sulfuric acid, 115-125 g / L sodium sulfate, and 4-5 g / L ferric chloride.

[0018] Furthermore, the oiling rate of the oiling is 1-1.2%, the heat setting is 110-120° C. hot air relaxation setting, and the setting time is 150±30s.

[0019] The beneficial effects of the present invention are:

[0020] This invention innovatively uses naringenin and tea polyphenols as antioxidants, loading these two antioxidants onto halloysite nanotubes after silanization modification with γ-aminopropyltriethoxysilane. Based on the principle of synergy, naringenin and tea polyphenols exhibit a synergistic antioxidant effect. Their combination can more effectively capture free radicals, exert antioxidant functions, and enhance the antioxidant properties of the fiber. The modification of the halloysite nanotubes with γ-aminopropyltriethoxysilane, on the one hand, introduces amino groups into the molecular nests, enabling them to form hydrogen bonds with the antioxidants, strengthening the binding force between the molecular nests and the antioxidants, effectively preventing the antioxidants from falling off 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, preventing moisture from hindering the silane modification reaction, improving the loading efficiency, and further ensuring the stability and effectiveness of the loading system. The construction of this antioxidant-loaded system, from antioxidant selection to carrier modification to the loading process, collaborates with each other to enhance the antioxidant performance and stability of the fiber. DETAILED DESCRIPTION

[0021] The technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described 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 of ordinary skill in the art without creative work are within the scope of protection of the present invention. The raw materials in the following examples are all commercially available.

[0022] Example 1

[0023] This embodiment provides a viscose biofiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts spinning solution, 10 parts molecular nests, 8 parts γ-glycidyloxypropyltrimethoxysilane, 7 parts sodium alginate, 5 parts sodium carboxymethyl cellulose, and 1405 parts water;

[0024] The method for preparing the viscose biofiber containing antioxidant active ingredients comprises 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 dried pre-treated halloysite nanotubes were dispersed in a mixed solution of 1050 mL of ethanol and 450 mL of water, ultrasonically treated at 280 W for 35 min, 11 g of γ-aminopropyltriethoxysilane was added, reacted at 60°C and 600 rpm for 5.5 h, centrifuged at 8000 rpm for 10 min, and the precipitate was washed three times with anhydrous ethanol. The alkylated halloysite nanotubes were obtained after vacuum drying at 60°C for 12 h.

[0026] 11 g of naringenin and 11 g of tea polyphenols were ultrasonically dispersed in 500 mL of anhydrous ethanol to obtain an antioxidant mixed solution; 100 g of halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane was immersed in the antioxidant mixed solution at -0.095 MPa and 40°C for 3.5 hours, filtered at normal pressure, and the solid was collected. The molecular nest was obtained after vacuum drying at 60°C for 6 hours.

[0027] The molecular nest is dispersed in water, and then γ-glycidyloxypropyltrimethoxysilane, sodium alginate and sodium carboxymethyl cellulose and a spinning solution containing 9.2wt% of cellulose and 3wt% of total alkali are added. The mixture is mixed at 45°C and 500rpm for 2.5h, filtered, degassed at 40°C for 2.5h, and aged at 18°C ​​for 44h to obtain a spinning solution with a viscosity of 46s. The spinning solution is introduced into a spinning machine and spun at a spinning speed of 17m / min. The spinning is kept in a coagulation bath at a temperature of 45°C for 22s. The contents of the components in the coagulation bath are: 80g / L sulfuric acid, 120g / L sodium sulfate, and 4.5g / L ferric chloride. After spinning and solidification, the viscose biofiber containing antioxidant active ingredients is obtained after desulfurization, washing with water at 62°C, oiling with an oiling rate controlled at 1.1%, and hot air relaxation and setting at 115°C for 150s.

[0028] Example 2

[0029] This embodiment provides a viscose biofiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts spinning solution, 9 parts molecular nests, 5 parts γ-glycidyloxypropyltrimethoxysilane, 6 parts sodium alginate, 4 parts sodium carboxymethyl cellulose, and 140 parts water;

[0030] The method for preparing the viscose biofiber containing antioxidant active ingredients comprises 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 dried pre-treated halloysite nanotubes were dispersed in a mixed solution of 1000 mL of ethanol and 400 mL of water, ultrasonically treated at 250 W for 30 min, 10 g of γ-aminopropyltriethoxysilane was added, reacted at 55° C. and 550 rpm for 5 h, centrifuged at 8000 rpm for 10 min, washed with anhydrous ethanol for 3 times, and dried in vacuo at 60° C. for 12 h to obtain alkylated halloysite nanotubes.

[0032] 10 g of naringenin and 10 g of tea polyphenols were ultrasonically dispersed in 480 mL of anhydrous ethanol to obtain an antioxidant mixed solution; 100 g of halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane were immersed in the antioxidant mixed solution at -0.095 MPa and 35°C for 3 hours, filtered at normal pressure, and the solid was collected. The molecular nest was obtained after vacuum drying at 60°C for 6 hours.

[0033] The molecular nest is dispersed in water, and then γ-glycidyloxypropyltrimethoxysilane, sodium alginate and sodium carboxymethyl cellulose and a spinning solution containing 9.1wt% of cellulose and 2.8wt% of total alkali are added. The mixture is mixed at 40°C and 450rpm for 2h, filtered, degassed at 35°C for 2h, and aged at 18°C ​​for 40h to obtain a spinning solution with a viscosity of 45s. The spinning solution is introduced into a spinning machine and spun at a spinning speed of 16m / min. The spinning is carried out in a coagulation bath at a temperature of 45°C for 20s. The contents of the components in the coagulation bath are: 75g / L sulfuric acid, 115g / L sodium sulfate, and 4g / L ferric chloride. After spinning and solidification, the viscose biofiber containing antioxidant active ingredients is obtained after desulfurization, washing with water at 60°C, oiling with an oiling rate of 1%, and hot air relaxation and shaping at 110 for 150s.

[0034] Example 3

[0035] This embodiment provides a viscose biofiber containing antioxidant active ingredients, comprising the following raw materials by weight: 1000 parts spinning solution, 11 parts molecular nests, 10 parts γ-glycidyloxypropyltrimethoxysilane, 8 parts sodium alginate, 6 parts sodium carboxymethyl cellulose, and 150 parts water;

[0036] The method for preparing the viscose biofiber containing antioxidant active ingredients comprises 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 dried pre-treated halloysite nanotubes were dispersed in a mixed solution of 1100 mL of ethanol and 500 mL of water, ultrasonically treated at 300 W for 40 min, 12 g of γ-aminopropyltriethoxysilane was added, and the mixture was reacted at 65° C. and 650 rpm for 6 h. The mixture was centrifuged at 8000 rpm for 10 min, and the precipitate was washed three times with anhydrous ethanol. The precipitate was then vacuum dried at 60° C. for 12 h to obtain the alkylated halloysite nanotubes.

[0038] 12 g of naringenin and 12 g of tea polyphenols were ultrasonically dispersed in 520 mL of anhydrous ethanol to obtain an antioxidant mixed solution; 100 g of halloysite nanotubes modified by alkylation with γ-aminopropyltriethoxysilane were immersed in the antioxidant mixed solution at -0.095 MPa and 45°C for 4 hours, filtered at normal pressure, and the solid was collected. The molecular nest was obtained after vacuum drying at 60°C for 6 hours.

[0039] The molecular nest is dispersed in water, and then γ-glycidyloxypropyltrimethoxysilane, sodium alginate and sodium carboxymethyl cellulose and a spinning solution containing 9.3wt% of methyl cellulose and 3.2wt% of total alkali are added. The mixture is mixed at 50°C and 550rpm for 3h, filtered, degassed at 45°C for 3h, and aged at 18°C ​​for 48h to obtain a spinning solution with a viscosity of 47s. The spinning solution is introduced into a spinning machine and spun at a spinning speed of 18m / min. The spinning is kept in a coagulation bath at a temperature of 45°C for 25s. The contents of the components in the coagulation bath are: 85g / L sulfuric acid, 125g / L sodium sulfate, and 5g / L ferric chloride. After spinning and solidification, the viscose biofiber containing antioxidant active ingredients is obtained after desulfurization, washing with water at 65°C, oiling with an oiling rate of 1.2%, and hot air relaxation and shaping at 120°C for 150s.

[0040] Comparative Example 1

[0041] Adjustments were made based on Example 1, except that the 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] Adjustments were made based on Example 1, except that the halloysite nanotubes were replaced with mesoporous silica (SBA-15) of equal mass.

[0044] Comparative Example 3

[0045] Adjustments were made based on Example 1, except that γ-aminopropyltriethoxysilane was replaced with a silane coupling agent KH570 of equal molar mass.

[0046] Comparative Example 4

[0047] Adjustments were made based on Example 1. The difference from Example 1 was that the halloysite nanotubes were not subjected to drying pretreatment during the preparation of the molecular nests.

[0048] Comparative Example 5

[0049] Adjustments were made based on Example 1. The difference from Example 1 was that the molecular nests were modified with silane during preparation, and the halloysite nanotubes after drying and pretreatment were directly impregnated with antioxidants. The preparation conditions were the same as those in Example 1.

[0050] Comparative Example 6

[0051] Adjustments were made based on Example 1, except that the naringenin in the antioxidant mixed solution was replaced with tea polyphenols of equal mass.

[0052] Comparative Example 7

[0053] Adjustments were made based on Example 1, except that the tea polyphenols in the antioxidant mixed solution were replaced with naringenin of equal mass.

[0054] Comparative Example 8

[0055] Adjustments were made based on Example 1, except that the molecular nests were replaced with halloysite nanotubes.

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

[0057] Mechanical properties test: The test method refers to GB / T 14344-2022 "Test method for tensile properties of chemical fiber filaments". No less than 30 specimens are tested and the test average value is taken;

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

[0059] Air permeability test: Refer to GB / T 5453-2025 "Determination of Air Permeability of Textile Fabrics" to test the air permeability;

[0060] Free radical scavenging rate: According to the detection method of DPPH free radical scavenging rate and ABTS + ·Testing by free radical scavenging rate detection method;

[0061] Antibacterial performance test: According to the method in GB / T20944.3-2008, the inhibition rate of each viscose biofiber containing antioxidant active ingredients against Staphylococcus aureus (ATCC6538), Escherichia coli (ATCC 8739), and Candida albicans (ATCC10231) was tested, and the inhibition rate after washing 100 times was tested.

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

[0063] Table 1

[0064]

[0065] Table 2

[0066]

[0067]

[0068] Combined with the above, Examples 1-3 demonstrate stable mechanical properties, with both dry fracture strength and hygroscopicity superior to the comparative example. Initial antibacterial rates for all three strains exceeded 92%, driven by the synergistic antioxidant effects of naringenin and tea polyphenols. Even after 100 washes and aging, the inhibition rate remained above 85%, demonstrating the high stability of the halloysite nanotube loading system. γ-aminopropyltriethoxysilane modification enhanced the binding of halloysite to the antioxidant, while pre-drying eliminated moisture interference and improved loading efficiency. In Comparative Example 1, the surface of the carbon nanotubes is smooth, the antioxidant loading rate is low and easy to fall off. Since the antioxidant cannot be effectively loaded / released, the free radical scavenging rate is close to 0; in Comparative Example 2, the pore size of the mesoporous silica is single, the antioxidant sustained-release effect is poor, and the mechanical strength is reduced; in Comparative Example 3, KH570 does not contain amino groups and cannot form hydrogen bonds with antioxidants. The weak binding force leads to easy loss; in Comparative Example 4, the residual moisture hinders the silane modification reaction without drying pretreatment, and the loading is uneven; in Comparative Example 5, the halloysite surface is directly loaded without silane modification, the hydrophilicity of the halloysite surface is weak, and the antioxidant adsorption amount is reduced by more than 60%; in Comparative Example 6, the phenolic hydroxyl group synergistic effect of naringenin is lacking, the antibacterial rate of Gram-positive bacteria is reduced by more than 10%, and the DPPH free radical / ABTS + The free radical scavenging rate was slightly reduced. In Comparative Example 7, the thermal stability of naringenin was poor, and the scavenging rate was significantly reduced. The release efficiency was reduced due to the fat solubility of naringenin. In Comparative Example 8, no antioxidant was loaded, no active ingredient was present, and the antibacterial performance was close to zero.

[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 the present invention can still be modified or replaced by equivalents. All technical solutions and improvements that do not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A viscose biofiber containing antioxidant active ingredients, characterized in that: The method comprises the following raw materials by weight: 1000 parts of spinning solution, 9-11 parts of molecular nests, 5-10 parts of gamma-glycidyloxypropyltrimethoxysilane, 6-8 parts of sodium alginate, 4-6 parts of sodium carboxymethyl cellulose and 140-150 parts of water.

2. The viscose biofiber containing antioxidant active ingredients according to claim 1, characterized in that: The preparation method of the molecular nest comprises: 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±0.005 MPa and 35-45° C. for 3-4 hours, filtering at normal pressure, collecting solids, and drying to obtain the product.

3. The viscose biofiber containing antioxidant active ingredients according to claim 2, characterized in that: The usage ratio of the naringenin, tea polyphenols, anhydrous ethanol and the halloysite nanotubes modified with a silane coupling agent is 10-12 g: 10-12 g: 480-520 mL: 100 g.

4. The viscose biofiber containing antioxidant active ingredients according to claim 2, characterized in that: The silanization modification step comprises: dispersing the dried pre-treated halloysite nanotubes in a mixed solution of ethanol and water, ultrasonically treating at 250-300W for 30-40min, adding γ-aminopropyltriethoxysilane and reacting at 55-65°C and 550-650rpm for 5-6h, centrifuging, washing and drying to obtain the product.

5. The viscose biofiber containing antioxidant active ingredients according to claim 4, characterized in that: The drying pretreatment step includes drying the halloysite nanotubes at a temperature of 100-110° C. and a pressure of -0.1±0.05 MPa for 4-5 hours.

6. The viscose biofiber containing antioxidant active ingredients according to claim 4, characterized in that: The usage ratio of the dried pretreated halloysite nanotubes, ethanol, water and γ-aminopropyltriethoxysilane is 100 g: 1000-1100 mL: 400-500 mL: 10-12 g.

7. The viscose biofiber containing antioxidant active ingredients according to claim 4, characterized in that: The inner diameter of the halloysite nanotube is 15 nm and the length is 1-2 μm.

8. A method for preparing a viscose biofiber containing antioxidant active ingredients according to any one of claims 1 to 7, characterized in that the steps include: The molecular nest is dispersed in water, and then γ-glycidyloxypropyltrimethoxysilane, sodium alginate and sodium carboxymethyl cellulose, as well as a spinning solution containing 9.1-9.3wt% of cellulose and 2.8-3.2wt% of total alkali are added. The mixture is mixed at 40-50°C and 450-550rpm for 2-3h, filtered, degassed at 35-45°C for 2-3h, and aged at 18±1°C for 40-48h to obtain a spinning solution with a viscosity of 45-47s. The spinning solution is introduced into a spinning machine and spun at a spinning speed of 16-18m / min. The fibers are spun into a coagulation bath at a temperature of 45±1°C and stay there for 20-25s. After spinning and solidification, the fibers are desulfurized, washed with water at 60-65°C, oiled, and heat-set to obtain a viscose biofiber containing antioxidant active ingredients.

9. The method for preparing the viscose biofiber containing antioxidant active ingredients according to claim 8, characterized in that: The contents of the components in the coagulation bath are: 75-85 g / L of sulfuric acid, 115-125 g / L of sodium sulfate, and 4-5 g / L of ferric chloride.

10. The method for preparing the viscose biofiber containing antioxidant active ingredients according to claim 8, characterized in that: The oiling rate of the oiling is 1-1.2%, the heat setting is 110-120° C. hot air relaxation setting, and the setting time is 150±30s.

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