Bionylon fiber containing antioxidant active ingredients and method for preparing the same

Abstract

A bio-nylon fiber containing an antioxidant active ingredient and a method for preparing the same are provided. [Solution] The method for preparing bio-nylon fiber containing antioxidant active ingredients includes the steps of preparing buckwheat leaf extract, preparing filipendula extract, preparing a porous base carrier, amination treatment, modification treatment, loading, preparing a functional masterbatch, and spinning. [Effects] The method for preparing bio-nylon fiber containing antioxidant active ingredients of the present invention can improve the binding performance of the plant extract active ingredients with antioxidant function with nylon fiber, effectively avoiding the problem of the plant extract active ingredients becoming less stable and easily inactivated during the acid dyeing process, effectively avoiding the problem of the plant extract active ingredients affecting the dyeing effect and causing uneven dyeing, and further improving the wash resistance and physical properties of nylon fiber.

Description

Technical Field

[0001] The present invention relates to the technical field of nylon fibers, and particularly to bio-nylon fibers containing antioxidant active components and a method for preparing the same.

Background Art

[0002] Nylon fiber, known as Polyamide in English and Nylon in scientific name, is also called Nylon. It is the world's first synthetic fiber, and its invention can be traced back to the 1930s and was created by American chemist Carothers and his scientific research group. The wear resistance of nylon fiber is very high, ranking first among all fibers, about 10 times that of cotton and about 20 times that of wool. Adding a small amount of nylon fiber to blended fibers can significantly improve the wear resistance of the fibers. At the same time, nylon fiber also has good strength, elasticity and hygroscopicity. Nylon fiber stretched to 103 - 106% has an elastic recovery rate of up to 100% of the fabric, which can withstand a certain amount of pressure and tensile force, and has a better wear feeling and touch than polyester woven clothes. In the prior art, nylon fiber is used in fields such as clothing, industrial production, and medical. In the field of clothing, due to its wear resistance, strength, and good elasticity, nylon fiber is widely used in the production of sportswear, outdoor wear, underwear, socks, etc. Also, nylon fiber can be blended with other fibers to make various styles of clothes. In the field of industrial production, due to the high strength and wear resistance of nylon fiber, it has become an ideal choice for industrial fabrics and is widely used in the manufacture of cord fabrics, cables, conveyor belts, fishing nets, etc.

[0003] With the development of science and technology and the improvement of living standards, the basic performance of nylon fiber has gradually failed to meet the requirements of various applications, and the research on improving the functionality of nylon has become increasingly numerous. The new development of functional nylon fiber has important significance for the functional research and the expansion of the application field of nylon fiber.

[0004] Tea contains antioxidants such as tea polyphenols and catechins, and orange peel contains antioxidants such as hesperidin and naringenin, and also, Itran Grapes contain antioxidants such as polyphenol compounds, flavonoids, and resveratrol, and possess ideal antioxidant properties. Prior art has already disclosed the use of plant extracts containing the above-mentioned antioxidants to modify the antioxidant functionality of nylon fibers. However, in modifying the antioxidant functionality of nylon fibers using plant extracts, the compatibility between the antioxidants in the plant extracts and the nylon fibers is poor. In the subsequent dyeing process of the nylon fibers, it is necessary to make them compatible with the dye in an acidic environment with a pH of 4-5 in order to obtain ideal dyeing results. As a result, not only is the stability of the antioxidants in the plant extracts reduced, but they also become more prone to failure, making it impossible to obtain the desired antioxidant properties, reducing the dyeing effect, and causing problems with uneven dyeing. At the same time, the antioxidants are easily lost during the process of washing the nylon fibers several times, resulting in poor washability. Furthermore, in modifying the antioxidant functionality of nylon fibers with plant extracts, the addition of plant extracts also affects the physical properties of the nylon fibers. [Overview of the project]

[0005] To solve the technical problems in the prior art, the present invention provides bionylon fiber containing antioxidant active components and a method for preparing the same, which can improve the binding performance between antioxidant active components of plant extracts and nylon fibers, effectively avoid the problem that the stability of the plant extract active components decreases and they are easily deactivated during the acid dyeing process, effectively avoid the problem that the plant extract active components affect the dyeing effect and cause uneven dyeing, and further improve the washability and physical performance of the nylon fibers.

[0006] To solve the above technical problems, the present invention provides the following technical solutions.

[0007] A method for preparing bionylon fibers containing antioxidant active ingredients involves preparing a buckwheat leaf extract, Itran The process includes each of the following steps: preparation of the extract, preparation of the porous base carrier, amination treatment, modification treatment, loading, preparation of the functional masterbatch, and spinning.

[0008] The steps for preparing the buckwheat leaf extract are as follows: Clean buckwheat leaves are frozen at -40°C to -35°C for 42 to 48 hours, then frozen again for 22 to 24 hours using a low-temperature freeze dryer, and then pulverized at 9000 to 10000 rpm to obtain buckwheat leaf powder with a particle size of 1700 to 1800 mesh. The buckwheat leaf powder is then added to 10 to 12 times its weight in an ethanol solution (volume concentration 55 to 60%), and a first ultrasonic extraction is performed for 15 to 20 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is added to 8 to 10 times its weight in an ethanol solution (volume concentration 55 to 60%), and a second ultrasonic extraction is performed for 10 to 15 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 42 to 45% of the original volume at 62 to 65°C in a vacuum environment of 0.06 to 0.07 MPa to prepare the buckwheat leaf extract.

[0009] In the preparation of the buckwheat leaf extract, the ultrasonic extraction temperature is controlled to 40-45°C, the ultrasonic extraction frequency is 41-43kHz, and the ultrasonic extraction power is 200-250W.

[0010] Buckwheat (Fagopyrum esculentum Moench), also known as oat or triangular oat, belongs to the genus Liao and is a dicotyledonous annual herbaceous plant. It prefers cool environments and is tolerant of poor soil. Buckwheat leaves are rich in flavonoids (such as rutin and quercetin), which are natural antioxidants with good antioxidant properties. The flavonoid content in buckwheat leaves is higher than that in buckwheat seeds. At the same time, buckwheat leaves also have antipyretic, antibacterial, and anti-inflammatory effects.

[0011] The aforementioned Itran The step of preparing the extract is to use a clean ItranThe stems and leaves were frozen at -40°C to -35°C for 42 to 48 hours, then frozen again for 22 to 24 hours using a low-temperature freeze dryer, and finally ground at 9000 to 10000 rpm to a particle size of 1700 to 1800 mesh. Itran Grind into a powder, then Itran The powder is placed in an ethanol solution (volume concentration 55-60%) 13-15 times its weight, and a first ultrasonic extraction is performed for 15-20 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is placed in an ethanol solution (volume concentration 55-60%) 10-12 times its weight, and a second ultrasonic extraction is performed for 10-15 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 58-60% of the original volume at 62-65°C under a vacuum of 0.06-0.07 MPa. Itran Prepare the extract.

[0012] The aforementioned Itran In preparing the extract, the ultrasonic extraction temperature is controlled to 40-45°C, the ultrasonic extraction frequency is 41-43 kHz, and the ultrasonic extraction power is 200-250 W.

[0013] Itran (Yucca smalliana Fern) has soft leaves. Itran Azabu Itran It is also known as the foreign pineapple and is a plant belonging to the genus Yucca in the family Asparagus. Itran The antioxidant active components in the stems and leaves mainly consist of flavonoids, polyphenols, saponins, etc., and these antioxidant active components can exert good antioxidant performance through different mechanisms, and simultaneously Itran It also has antibacterial, detoxifying, and anti-inflammatory properties.

[0014] The steps for preparing the porous base carrier are as follows: 2-methylimidazole is added to 18-20 times its weight in anhydrous methanol, stirred and dissolved to prepare the first solution; zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 22-24 times its weight in anhydrous methanol, stirred and dissolved to prepare the second liquid; the second liquid is added to the first liquid under stirring conditions, stirred at room temperature for 50-60 minutes, then allowed to stand for 20-30 minutes to obtain the reaction solution; centrifuged at 11000-12000 rpm to obtain a solid; the solid is washed with 2-2.5 times its weight in anhydrous methanol, then placed in a vacuum drying box, dried at 65-70°C in a vacuum environment of 0.085-0.095 MPa until it reaches a certain weight, and then uniformly polished to prepare the porous base carrier.

[0015] In the preparation of the porous base carrier, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate is 2.2-2.3:0.7-0.8:0.35-0.4.

[0016] The amination treatment step involves placing the porous base carrier into an ethanol solution (volume concentration 75-80%) 6-7 times its weight, ultrasonically dispersing it for 5-10 minutes, stirring to raise the temperature to 40-45°C, maintaining the temperature and stirring for 10-15 minutes, then dropping the bisaminosilane coupling agent A-2120 while stirring, controlling the dropping time of the bisaminosilane coupling agent A-2120 to 40-50 minutes, and after the dropping is completed, maintaining the temperature and stirring for 5-6 hours, then centrifuging at 11000-12000 rpm to obtain a solid, washing the solid with 2.5-3 times its weight of deionized water, placing it in a vacuum drying box, drying it to a certain weight at 90-95°C in a vacuum environment of 0.085-0.095 MPa, uniformly polishing it, and preparing the amination carrier.

[0017] In the amination treatment described above, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 is 1:0.16 to 0.19.

[0018] The steps of the modification treatment are as follows: Put hexanedioyl chloride into a reaction kettle equipped with tetrahydrofuran, stir and dissolve it, then replace the air in the reaction kettle with nitrogen, put the aminated carrier into it while stirring, stir at room temperature for 10 - 12 h, then centrifuge at 11000 - 12000 rpm to obtain a solid substance. After washing the solid substance with 1.5 - 1.8 times its weight of tetrahydrofuran, filter it and put it into a reaction kettle equipped with N,N - dimethylformamide. Replace the air in the reaction kettle with nitrogen, put 1,2 - ethyldisulfide and triethylamine into it while stirring, stir at room temperature for 5 - 6 h, then centrifuge at 11000 - 12000 rpm to obtain a solid substance. Wash the solid substance 2 - 3 times with 3 - 3.5 times its weight of deionized water, then put it into a vacuum drying box, and dry it to a constant weight at 110 - 120 °C in an environment with a vacuum degree of 0.085 - 0.095 MPa, and uniformly polish it to prepare a modified carrier.

[0019] In the modification treatment, the weight ratio of hexanedioyl chloride, aminated carrier, 1,2 - ethyldisulfide, and triethylamine is 4 - 4.2:25 - 26:0.5 - 0.55:0.9 - 0.95. The weight ratio of the aminated carrier to tetrahydrofuran is 1:8 - 9. The weight ratio of the aminated carrier to N,N - dimethylformamide is 1:4 - 5.

[0020] The steps of the loading are as follows: Mix the buckwheat leaf extract and Itran the extract in equal volumes uniformly to prepare a loading solution. Then put the modified carrier into the loading solution, disperse it by ultrasonic wave for 10 - 20 min, then stir and heat it up to 35 - 40 °C, keep it warm and stir for 5 - 6 h, then centrifuge at 11000 - 12000 rpm to obtain a solid substance. After washing the solid substance with 3 - 3.5 times its weight of deionized water, put it into a vacuum drying box, and dry it to a constant weight at 80 - 85 °C in an environment with a vacuum degree of 0.04 - 0.05 MPa, and uniformly polish it to prepare a composite active ingredient.

[0021] In the steps of the loading, the weight ratio of the modified carrier to the loading solution is 1:6 - 6.5. The method for preparing the functional masterbatch is to put the composite active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate into a twin-screw extruder, heat up to 260-265 °C, keep warm and melt for 25-35 min, and then extrude and granulate to prepare the functional masterbatch.

[0022] In the preparation of the functional masterbatch, the weight ratio of the composite active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate is 11-12:83-86:0.9-1.1:0.7-0.8:0.65-0.75.

[0023] The spinning step is to put nylon 66 slices and the functional masterbatch into a spinning melting device, extrude and melt in a temperature environment of 260-265 °C, then spin using a screw spinning machine, control the spinning speed at 1700-1850 m / min, and then perform stretching, oiling, and winding to prepare bio-nylon fibers containing antioxidant active ingredients.

[0024] In the spinning, the weight ratio of nylon 66 slices to the functional masterbatch is 100:11-12.

[0025] The bio-nylon fibers containing antioxidant active ingredients are prepared by the above preparation method.

Effects of the Invention

[0026] Compared with the prior art, the present invention has the following beneficial effects.

[0027] (1) The preparation method of the bio-nylon fibers containing antioxidant active ingredients of the present invention is based on the characteristics of nylon fibers and buckwheat leaves, ItranIn light of the characteristics of the antioxidant active components contained therein, in each step of preparing the porous base carrier, a Zn / Ce bimetallic component is combined and used in combination with the organic ligand 2-methylimidazole to improve the active site in the prepared porous base carrier through the synergistic coordination effect of the Zn / Ce bimetallic active center, thereby improving the binding stability with the antioxidant active components thereafter. Subsequently, in the amination step, the porous base carrier is aminated using a bisaminosilane coupling agent to effectively introduce amino groups, thereby improving the effect of the subsequent modification treatment, ensuring the binding effect between the modified carrier and the antioxidant active components, and improving the stability of the antioxidant active components in the nylon fiber, while also improving the compatibility and binding performance between the composite active components containing antioxidant active components and nylon. In the subsequent modification step, the aminated carrier is subjected to sulfhydryl modification to further improve the binding stability and durability between the modified carrier and the antioxidant active components, and further improve the functional stability in the nylon fiber. In the subsequent loading step, a buckwheat leaf extract containing antioxidant active components such as flavonoids and polyphenols is added. Itran Select the extract, and the buckwheat leaf extract and Itran After mixing the extracts to form a support solution, an adsorption and binding process is carried out using a modified carrier to prepare a complex active ingredient. Subsequently, a functional masterbatch is prepared using the complex active ingredient, and then spun in combination with nylon raw material to prepare bio-nylon fibers containing antioxidant active ingredients. As a result, the binding performance between the plant extract active ingredients with antioxidant function and the nylon fibers is improved, the problem of decreased stability and deactivation of antioxidant active ingredients during the acid dyeing process is effectively avoided, the problem of the antioxidant active ingredients affecting the dyeing effect and causing uneven dyeing is effectively avoided, and the wash resistance and physical performance of the bio-nylon fibers can be further improved.

[0028] (2) The bionylon fiber containing the antioxidant active component of the present invention has a DPPH radical removal rate of 90.0-90.4%, an ABTS+ radical removal rate of 88.4-88.7%, a hydroxyl radical removal rate of 80.9-81.2%, a breaking strength of 5.8-6.1 cN / dtex, and a breaking elongation of 24.8-25.1%.

[0029] (3) The bionylon fiber containing the antioxidant active component of the present invention has a bacterial inhibition rate of 99.3-99.5% against Staphylococcus aureus, a bacterial inhibition rate of 98.7-99.0% against Escherichia coli, and a bacterial inhibition rate of 95.3-95.6% against Candida albicans.

[0030] (4) The bionylon fiber containing the antioxidant active component of the present invention has a dyeing rate of 97.1 to 97.3%, a semi-dyeing time extension rate of 3.8 to 4.0%, a dye color difference value △E of 0.03 to 0.04, and a soap fastness of grade 4.

[0031] (5) The bionylon fibers containing the antioxidant active component of the present invention have a DPPH radical removal rate of 89.2-89.7% after dyeing, an ABTS+ radical removal rate of 87.6-88.1%, a hydroxyl radical removal rate of 80.0-80.4%, a bacterial inhibition rate against Staphylococcus aureus of 98.1-98.5%, a bacterial inhibition rate against Escherichia coli of 97.7-98.1%, and a bacterial inhibition rate against Candida albicans of 94.1-94.5%.

[0032] (6) The bio-nylon fiber containing the antioxidant active component of the present invention has a DPPH radical removal rate of 83.0-83.6% after being washed 20 times, an ABTS+ radical removal rate of 81.4-81.9%, a hydroxyl radical removal rate of 74.8-75.2%, a bacterial inhibition rate against Staphylococcus aureus of 90.7-91.4%, a bacterial inhibition rate against Escherichia coli of 90.6-91.0%, and a bacterial inhibition rate against Candida albicans of 87.4-87.7%. [Modes for carrying out the invention]

[0033] To more clearly explain the technical features, objectives, and effects of the present invention, specific embodiments of the present invention will be described.

[0034] <Example 1> This embodiment provides a method for preparing bionylon fibers containing antioxidant active components, specifically as follows: 1. Preparation of buckwheat leaf extract Clean buckwheat leaves are frozen at -40°C for 42 hours, then frozen again for 22 hours using a low-temperature freeze-dryer. After that, they are ground at 9000 rpm to obtain buckwheat leaf powder with a particle size of 1700 mesh. The buckwheat leaf powder is then added to 10 times its weight in an ethanol solution (55% volume concentration), and the first ultrasonic extraction is performed for 15 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is added to 8 times its weight in an ethanol solution (55% volume concentration), and the second ultrasonic extraction is performed for 10 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 42% of the original volume at 62°C under a vacuum of 0.06 MPa to prepare the buckwheat leaf extract. Here, the ultrasonic extraction temperature is controlled to 40°C, the ultrasonic extraction frequency is 41kHz, and the ultrasonic extraction power is 200W.

[0035] 2. Itran Preparation of the extract pure Itran The stems and leaves were frozen at -40°C for 42 hours, then frozen again for 22 hours using a low-temperature freeze-dryer, and finally ground at 9000 rpm to a particle size of 1700 mesh. Itran Grind into a powder, then Itran The powder is placed in a 13-fold weight ethanol solution (55% volume concentration), and the first ultrasonic extraction is performed for 15 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is placed in a 10-fold weight ethanol solution (55% volume concentration), and the second ultrasonic extraction is performed for 10 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 58% of the original volume at 62°C under a vacuum of 0.06 MPa. Itran Prepare the extract. Here, the ultrasonic extraction temperature is controlled to 40°C, the ultrasonic extraction frequency is 41kHz, and the ultrasonic extraction power is 200W.

[0036] 3. Preparation of porous base carrier 2-methylimidazole is added to 18 times its weight in anhydrous methanol, stirred and dissolved to prepare the first solution. Zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 22 times its weight in anhydrous methanol, stirred and dissolved to prepare the second liquid. Under stirring conditions, the second liquid is added to the first liquid, stirred at room temperature for 50 minutes, then allowed to stand for 20 minutes to obtain the reaction solution. The mixture is centrifuged at 11000 rpm to obtain a solid. The solid is washed with twice its weight in anhydrous methanol, then placed in a vacuum drying box and dried at 65°C in a vacuum of 0.085 MPa until it reaches a certain weight. It is then uniformly polished to prepare a porous base carrier. Here, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate is 2.2:0.7:0.35.

[0037] 4. Amination treatment The porous base carrier is placed in a 6x weight ethanol solution (volume concentration 75%), ultrasonically dispersed for 5 minutes, stirred, and heated to 40°C. After stirring and maintaining the temperature for 10 minutes, bisaminosilane coupling agent A-2120 is added dropwise while stirring, controlling the addition time of bisaminosilane coupling agent A-2120 to 40 minutes. After the addition is completed, the mixture is continuously stirred and maintained at the temperature for 5 hours, then centrifuged at 11000 rpm to obtain a solid. The solid is washed with 2.5x weight deionized water, placed in a vacuum drying box, and dried at 90°C in a vacuum of 0.085 MPa until it reaches a certain weight. It is then uniformly polished to prepare the amination carrier. Here, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 is 1:0.16.

[0038] 5. Modification treatment Hexanedioyl chloride is placed in a reaction vessel equipped with tetrahydrofuran, stirred and dissolved, then the air in the reaction vessel is replaced with nitrogen, and the amination support is added while stirring. After stirring at room temperature for 10 hours, the mixture is centrifuged at 11000 rpm to obtain a solid. The solid is washed with 1.5 times its weight of tetrahydrofuran, filtered, and placed in a reaction vessel equipped with N,N-dimethylformamide. The air in the reaction vessel is replaced with nitrogen, and 1,2-ethyl disulfide and triethylamine are added while stirring. After stirring at room temperature for 5 hours, the mixture is centrifuged at 11000 rpm to obtain a solid. The solid is washed three times with 3 times its weight of deionized water, then placed in a vacuum drying box and dried at 110°C in a vacuum of 0.085 MPa until it reaches a certain weight, and then uniformly polished to prepare the modified support. Here, the weight ratio of hexanedioil chloride, amination carrier, 1,2-ethyl disulfide, and triethylamine is 4:25:0.5:0.9. The weight ratio of the amination carrier to the tetrahydrofuran is 1:8. The weight ratio of the amination carrier to N,N-dimethylformamide is 1:4.

[0039] 6. Carrying Buckwheat leaf extract and Itran The extracts are uniformly mixed in equal volumes to prepare a support solution. Then, the modified support is added to the support solution and ultrasonically dispersed for 10 minutes. After stirring, the mixture is heated to 35°C and kept warm and stirred for 5 hours. The mixture is then centrifuged at 11,000 rpm to obtain a solid. The solid is washed with three times its weight in deionized water, placed in a vacuum drying box, and dried at 80°C in a vacuum environment of 0.04 MPa until it reaches a certain weight. Finally, it is uniformly polished to prepare the composite active ingredient. Here, the weight ratio of the modified carrier to the supported liquid is 1:6.

[0040] 7. Preparation of functional masterbatch A complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate are placed in a twin-screw extruder, heated to 260°C, and kept warm for 25 minutes until melted. The mixture is then extruded and granulated to prepare a functional masterbatch. Here, the weight ratio of the complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate is 11:83:0.9:0.7:0.65.

[0041] 8. Spinning Nylon 66 slices and a functional masterbatch are placed in a spinning and melting apparatus, extruded and melted at a temperature of 260°C, then spun using a screw spinning machine with the spinning speed controlled to 1700 m / min, followed by stretching, application of an oil, and winding to prepare bio-nylon fibers containing antioxidant active components. Here, the weight ratio of nylon 66 slices to the functional masterbatch is 100:11.

[0042] This embodiment further provides bionylon fibers containing antioxidant active components, which are prepared by the above preparation method.

[0043] <Example 2> This embodiment provides a method for preparing bionylon fibers containing antioxidant active components, specifically as follows: 1. Preparation of buckwheat leaf extract Clean buckwheat leaves are frozen at -38°C for 45 hours, then frozen again for 23 hours using a low-temperature freeze-dryer. After that, they are ground at 9500 rpm to obtain buckwheat leaf powder with a particle size of 1750 mesh. The buckwheat leaf powder is then added to an 11-fold weight ethanol solution (57% volume concentration), and the first ultrasonic extraction is performed for 18 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is added to an 9-fold weight ethanol solution (57% volume concentration), and the second ultrasonic extraction is performed for 12 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 43% of the original volume at 63°C under a vacuum of 0.065 MPa to prepare the buckwheat leaf extract. Here, the ultrasonic extraction temperature is controlled to 42°C, the ultrasonic extraction frequency is 42kHz, and the ultrasonic extraction power is 240W.

[0044] 2. Itran Preparation of the extract pure ItranThe stems and leaves were frozen at -38°C for 45 hours, then frozen again for 23 hours using a low-temperature freeze-dryer, and finally ground at 9500 rpm to a particle size of 1750 mesh. Itran Grind into a powder, then Itran The powder was placed in a 14-fold weight ethanol solution (57% volume concentration), and the first ultrasonic extraction was performed for 18 minutes. The mixture was then filtered to obtain the first extract. The filtered residue was placed in an 11-fold weight ethanol solution (57% volume concentration), and the second ultrasonic extraction was performed for 12 minutes. The mixture was then filtered to obtain the second extract. After mixing the first and second extracts, the mixture was concentrated to 59% of its original volume at 63°C under a vacuum of 0.065 MPa. Itran Prepare the extract. Here, the ultrasonic extraction temperature is controlled to 42°C, the ultrasonic extraction frequency is 42kHz, and the ultrasonic extraction power is 240W.

[0045] 3. Preparation of porous base carrier 2-methylimidazole is added to 19 times its weight in anhydrous methanol, stirred and dissolved to prepare the first solution. Zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 23 times its weight in anhydrous methanol, stirred and dissolved to prepare the second liquid. Under stirring conditions, the second liquid is added to the first liquid, stirred at room temperature for 55 minutes, then allowed to stand for 25 minutes to obtain the reaction solution. The solid is obtained by centrifugation at 11500 rpm, washed with 2.3 times its weight in anhydrous methanol, placed in a vacuum drying box, dried at 68°C in a vacuum of 0.09 MPa until it reaches a certain weight, and then uniformly polished to prepare a porous base carrier. Here, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate is 2.25:0.75:0.38.

[0046] 4. Amination treatment The porous base carrier is placed in a 6.5-fold weight ethanol solution (volume concentration 78%), ultrasonically dispersed for 8 minutes, then stirred and heated to 42°C. After 12 minutes of heating and stirring, bisaminosilane coupling agent A-2120 is added dropwise while stirring, controlling the addition time of bisaminosilane coupling agent A-2120 to 45 minutes. After the addition is completed, the mixture is continuously heated and stirred for 5.5 hours, then centrifuged at 11500 rpm to obtain a solid. The solid is washed with 2.8-fold weight deionized water, placed in a vacuum drying box, dried at 92°C in a vacuum of 0.09 MPa until it reaches a certain weight, and then uniformly polished to prepare the amination carrier. Here, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 is 1:0.18.

[0047] 5. Modification treatment Hexanedioyl chloride is placed in a reaction vessel equipped with tetrahydrofuran, stirred and dissolved, then the air in the reaction vessel is replaced with nitrogen, and the amination support is added while stirring. After stirring at room temperature for 11 hours, the mixture is centrifuged at 11500 rpm to obtain a solid. The solid is washed with 1.6 times its weight in tetrahydrofuran, filtered, and placed in a reaction vessel equipped with N,N-dimethylformamide. The air in the reaction vessel is replaced with nitrogen, and 1,2-ethyl disulfide and triethylamine are added while stirring. After stirring at room temperature for 5.5 hours, the mixture is centrifuged at 11500 rpm to obtain a solid. The solid is washed three times with 3.2 times its weight in deionized water, then placed in a vacuum drying box and dried at 115°C in a vacuum of 0.09 MPa until it reaches a certain weight, then uniformly polished to prepare the modified support. Here, the weight ratio of hexanedioil chloride, amination carrier, 1,2-ethyl disulfide, and triethylamine is 4.1:25.5:0.53:0.92. The weight ratio of the amination carrier to the tetrahydrofuran is 1:8.5. The weight ratio of the amination carrier to N,N-dimethylformamide is 1:4.5.

[0048] 6. Carrying Buckwheat leaf extract and ItranThe extracts are uniformly mixed in equal volumes to prepare a support solution. Then, the modified support is added to the support solution and ultrasonically dispersed for 15 minutes. After stirring, the mixture is heated to 38°C and kept warm and stirred for 5.5 hours. The mixture is then centrifuged at 11500 rpm to obtain a solid. The solid is washed with 3.2 times its weight in deionized water, placed in a vacuum drying box, and dried at 83°C in a vacuum environment of 0.045 MPa until it reaches a certain weight. Finally, it is uniformly polished to prepare the composite active ingredient. Here, the weight ratio of the modified carrier to the supported liquid is 1:6.3.

[0049] 7. Preparation of functional masterbatch A complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate are placed in a twin-screw extruder, heated to 263°C, and kept warm for 30 minutes until melted. The mixture is then extruded and granulated to prepare a functional masterbatch. Here, the weight ratio of the complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate is 11.5:85:1:0.75:0.7.

[0050] 8. Spinning Nylon 66 slices and a functional masterbatch are placed in a spinning and melting apparatus, extruded and melted at a temperature of 263°C, then spun using a screw spinning machine with the spinning speed controlled to 1800 m / min, followed by stretching, application of an oil, and winding to prepare bio-nylon fibers containing antioxidant active components. Here, the weight ratio of nylon 66 slices to the functional masterbatch is 100:11.7.

[0051] This embodiment further provides bionylon fibers containing antioxidant active components, which are prepared by the above preparation method.

[0052] <Example 3> This embodiment provides a method for preparing bionylon fibers containing antioxidant active components, specifically as follows: 1. Preparation of buckwheat leaf extract Clean buckwheat leaves are frozen at -35°C for 48 hours, then frozen again for 24 hours using a low-temperature freeze-dryer. After that, they are ground at 10,000 rpm to obtain buckwheat leaf powder with a particle size of 1,800 mesh. The buckwheat leaf powder is then added to 12 times its weight in an ethanol solution (60% volume concentration), and the first ultrasonic extraction is performed for 20 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is added to 10 times its weight in an ethanol solution (60% volume concentration), and the second ultrasonic extraction is performed for 15 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 45% of the original volume at 65°C under a vacuum of 0.07 MPa to prepare the buckwheat leaf extract. Here, the ultrasonic extraction temperature is controlled to 45°C, the ultrasonic extraction frequency is 43kHz, and the ultrasonic extraction power is 250W.

[0053] 2. Itran Preparation of the extract pure Itran The stems and leaves were frozen at -35°C for 48 hours, then frozen again for 24 hours using a low-temperature freeze-dryer, and finally ground at 10,000 rpm to a particle size of 1800 mesh. Itran Grind into a powder, then Itran The powder is placed in a 15-fold weight ethanol solution (60% volume concentration), and the first ultrasonic extraction is performed for 20 minutes. The mixture is then filtered to obtain the first extract. The filtered residue is placed in a 12-fold weight ethanol solution (60% volume concentration), and the second ultrasonic extraction is performed for 15 minutes. The mixture is then filtered to obtain the second extract. The first and second extracts are mixed, and then concentrated to 60% of the original volume at 65°C under a vacuum of 0.07 MPa. Itran Prepare the extract. Here, the ultrasonic extraction temperature is controlled to 45°C, the ultrasonic extraction frequency is 43kHz, and the ultrasonic extraction power is 250W.

[0054] 3. Preparation of porous base carrier 2-methylimidazole is added to 20 times its weight in anhydrous methanol, stirred and dissolved to prepare the first solution. Zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 24 times its weight in anhydrous methanol, stirred and dissolved to prepare the second liquid. Under stirring conditions, the second liquid is added to the first liquid, stirred at room temperature for 60 minutes, then allowed to stand for 30 minutes to obtain the reaction solution. The solid is obtained by centrifugation at 12000 rpm, washed with 2.5 times its weight in anhydrous methanol, placed in a vacuum drying box, dried at 70°C in a vacuum of 0.095 MPa until it reaches a certain weight, and then uniformly polished to prepare a porous base carrier. Here, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate is 2.3:0.8:0.4.

[0055] 4. Amination treatment The porous base carrier is placed in a 7-fold weight ethanol solution (80% volume concentration), ultrasonically dispersed for 10 minutes, then stirred and heated to 45°C, kept warm and stirred for 15 minutes, and while stirring, bisaminosilane coupling agent A-2120 is added dropwise, controlling the addition time of bisaminosilane coupling agent A-2120 to 50 minutes. After the addition is completed, the mixture is kept warm and stirred for 6 hours, then centrifuged at 12000 rpm to obtain a solid, washed with 3-fold weight deionized water, placed in a vacuum drying box, dried at 95°C in a vacuum of 0.095 MPa until it reaches a certain weight, uniformly polished, and prepared as an amination carrier. Here, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 is 1:0.19.

[0056] 5. Modification treatment Hexanedioyl chloride is placed in a reaction vessel equipped with tetrahydrofuran, stirred and dissolved, then the air in the reaction vessel is replaced with nitrogen, and the amination support is added while stirring. After stirring at room temperature for 12 hours, the mixture is centrifuged at 12,000 rpm to obtain a solid. The solid is washed with 1.8 times its weight in tetrahydrofuran, filtered, and placed in a reaction vessel containing N,N-dimethylformamide. The air in the reaction vessel is replaced with nitrogen, and 1,2-ethyl disulfide and triethylamine are added while stirring. After stirring at room temperature for 6 hours, the mixture is centrifuged at 12,000 rpm to obtain a solid. The solid is washed three times with 3.5 times its weight in deionized water, then placed in a vacuum drying box and dried at 120°C in a vacuum of 0.095 MPa until it reaches a certain weight. It is then uniformly polished to prepare the modified support. Here, the weight ratio of hexanedioil chloride, amination carrier, 1,2-ethyl disulfide, and triethylamine is 4.2:26:0.55:0.95. The weight ratio of the amination carrier to the tetrahydrofuran is 1:9. The weight ratio of the amination carrier to N,N-dimethylformamide is 1:5.

[0057] 6. Carrying Buckwheat leaf extract and Itran The extracts are uniformly mixed in equal volumes to prepare a support solution. Then, the modified support is added to the support solution and ultrasonically dispersed for 20 minutes. After stirring, the mixture is heated to 40°C and kept warm and stirred for 6 hours. The mixture is then centrifuged at 12,000 rpm to obtain a solid. The solid is washed with 3.5 times its weight in deionized water, placed in a vacuum drying box, and dried at 85°C in a vacuum environment of 0.05 MPa until it reaches a certain weight. Finally, it is uniformly polished to prepare the composite active ingredient. Here, the weight ratio of the modified carrier to the supported liquid is 1:6.5.

[0058] 7. Preparation of functional masterbatch A complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate are placed in a twin-screw extruder, heated to 265°C, and kept warm for 35 minutes until melted. The mixture is then extruded and granulated to prepare a functional masterbatch. Here, the weight ratio of the complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate is 12:86:1.1:0.8:0.75.

[0059] 8. Spinning Nylon 66 slices and a functional masterbatch are placed in a spinning and melting apparatus, extruded and melted at a temperature of 265°C, then spun using a screw spinning machine with the spinning speed controlled to 1850 m / min, followed by stretching, application of an oil, and winding to prepare bio-nylon fibers containing antioxidant active components. Here, the weight ratio of nylon 66 slices to the functional masterbatch is 100:12.

[0060] This embodiment further provides bionylon fibers containing antioxidant active components, which are prepared by the above preparation method. <Comparative Example 1> The technical solution of Example 2 was adopted, with the following differences: 1) The step of preparing the buckwheat leaf extract was omitted, and in the subsequent loading step, Itran The extract is used as the support solution, and in step 2) the amination treatment, the silane coupling agent KH-550 is used instead of the bisaminosilane coupling agent A-2120.

[0061] <Comparative Example 2> The technical solution of Example 2 was adopted, with the following differences: 1) The step of preparing the porous base carrier was omitted, and 3A zeolite powder was used instead of the porous base carrier in the subsequent steps. 2) The amination step was omitted, and dried 3A zeolite powder was used directly in the modification step.

[0062] <Comparative Example 3> The technical solution of Example 2 was adopted, with the following differences: 1) In the step of preparing the porous base carrier, the addition of cerium nitrate hexahydrate was omitted, and the molar ratio of 2-methylimidazole to zinc nitrate hexahydrate was controlled to 2.25:1.05. 2) The modification step was omitted, and the amination carrier prepared in the amination treatment was used directly in the loading step.

[0063] The antioxidant performance and physical properties of the nylon fibers in Examples 1-3 and Comparative Examples 1-3 were detected, and specifically, the DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, breaking strength, and breaking elongation of each nylon fiber were detected.

[0064] Specifically, the method for detecting the DPPH radical removal rate is as follows: Weigh 2.5 mg of 1,1-diphenyl-2-trinitrophenylhydrazine DPPH, dissolve it in an appropriate amount of anhydrous ethanol, shake well away from light to completely dissolve it, then add anhydrous ethanol to a final volume of 100.0 mL to prepare a DPPH ethanol solution with a concentration of 25.0 mg / L.

[0065] 2.0 g of nylon fiber from Examples 1-3 and Comparative Examples 1-3 was weighed and placed in an ultrasonic extraction bottle containing 50 mL of ethanol solution (60% volume concentration). After immersion for 16 hours, ultrasonic extraction was performed for 10 minutes. The filtrate was then filtered and collected using a Büchner funnel. The filtrate was transferred to a rotary evaporator, the rotational evaporation temperature was controlled to 55°C, and the rotational evaporation vacuum was 0.085 MPa. Rotary evaporation continued until the filtrate reached 2 mL, at which point the rotational evaporation was stopped. The ethanol solution (60% volume concentration) was diluted to 4 mL to prepare the test solution.

[0066] Add 1 mL of the test solution to 2 mL of DPPH ethanol solution, mix uniformly, and let stand for 10 minutes away from light. Then, detect the absorbance at a wavelength of 517 nm using a spectrophotometer and calculate the DPPH radical removal rate.

[0067] The method for detecting the ABTS+ radical removal rate is as follows: Weigh 200.0 mg of 2,2-biazobis(3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt ABTS and 34.4 mg of potassium persulfate, dissolve them in 50.0 mL of deionized water, and leave at room temperature away from light for 24 hours to obtain the ABTS mother liquor. Take an appropriate amount of the ABTS mother liquor and dilute it with a 95% volume ethanol solution until the absorbance value at a wavelength of 734 nm is 0.70 to obtain the ABTS diluent.

[0068] The test solution is prepared, and the specific method is the same as the method for preparing the test solution in the DPPH radical removal rate detection described above.

[0069] Add 0.5 mL of the test solution to 5 mL of ABTS diluent, mix uniformly, and let stand for 10 minutes away from light. Then, detect the absorbance at a wavelength of 734 nm using a spectrophotometer and calculate the ABTS+ radical removal rate.

[0070] The hydroxyl radical removal rate is detected by the o-diazafil method.

[0071] For specific methods of detecting breaking strength and breaking elongation, refer to the national standard GB / T14344-2022, "Test Methods for Tensile Performance of Chemical Fiber Filaments." The specific results are shown in the table below: JPEG0007881675000001.jpg53170

[0072] Furthermore, the antibacterial properties of the nylon fibers in Examples 1-3 and Comparative Examples 1-3 were detected, and the specific methods should be referred to the relevant provisions in GB / T20944.3-2008 "Evaluation of Antibacterial Properties of Textiles, Part 3: Vibration Method".

[0073] The bacterial species used for detecting antimicrobial performance are Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 8739), and Candida albicans (ATCC 10231). The specific results are shown in the table below: JPEG0007881675000002.jpg67170

[0074] Furthermore, the nylon fibers of Examples 1-3 and Comparative Examples 1-3 were dyed, and the dyeing rate, extension rate of the semi-dyeing time, the color difference value, and the soap fastness were detected. Here, the extension rate of the semi-dyeing time was calculated using the semi-dyeing time of conventional nylon 66 fibers as the reference value, and calculated based on the semi-dyeing time of the nylon fibers of Examples 1-3 and Comparative Examples 1-3, to which the antioxidant active component was added, and the effect on the dyeing performance after modifying the nylon fibers using the antioxidant active component (i.e., the composite active component) of the present invention was evaluated.

[0075] The calculation method for the extension rate of the semi-staining time is as follows: [(Semi-staining time after modification of nylon fibers with antioxidant active ingredients - standard value) / standard value] × 100%. The specific results are shown in the table below: JPEG0007881675000003.jpg64170

[0076] Furthermore, the DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, and antibacterial performance of the nylon fibers of Examples 1-3 and Comparative Examples 1-3 after dyeing were detected, and the specific results are shown in the table below: JPEG0007881675000004.jpg131170

[0077] Furthermore, after pure spinning the nylon fibers of Examples 1-3 and Comparative Examples 1-3 into fabric, they were cut into 20cm x 20cm washing samples. Each washing sample was placed in a washing machine, the water temperature was set to 45°C, and one wash cycle was defined as 30 minutes. After washing, the samples were air-dried in a constant temperature environment of 35°C. The washing-drying process was repeated 20 times. After dyeing each nylon fiber, the DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, and antibacterial performance were detected. The specific results are shown in the table below: JPEG0007881675000005.jpg131170

[0078] As can be seen from the table above, the method for preparing bionylon fibers containing antioxidant active components of the present invention involves, in the step of preparing a porous base carrier, combining a Zn / Ce bimetallic component with the organic ligand 2-methylimidazole to improve the active site in the prepared porous base carrier through the synergistic coordination effect of the Zn / Ce bimetallic active center, thereby improving the binding stability with the antioxidant active component thereafter. Subsequently, in the amination treatment step, the porous base carrier is aminated using a bisaminosilane coupling agent to effectively convert the amino groups. This is introduced to improve the effect of subsequent modification treatments, ensure the binding effect between the modified carrier and the antioxidant active component, improve the stability of the antioxidant active component in nylon fibers, and improve the compatibility and binding performance between the composite active component containing the antioxidant active component and nylon. In the subsequent modification treatment step, the amination carrier is subjected to sulfhydryl modification treatment to further improve the binding stability and durability of the modified carrier and the antioxidant active component, further improving the functional stability in nylon fibers. In the subsequent loading step, a buckwheat leaf extract containing antioxidant active components such as flavonoids and polyphenols is used. Itran Select the extract, and the buckwheat leaf extract and ItranAfter mixing the extracts to form a support solution, an adsorption and binding process is carried out using a modified support to prepare a complex active ingredient. Subsequently, a functional masterbatch is prepared using the complex active ingredient, and then spun in combination with nylon raw material to prepare bionylon fibers containing antioxidant active ingredients. The binding performance between the complex active ingredient and the bionylon fibers is effectively improved, imparting antioxidant and antibacterial properties to the bionylon fibers. The DPPH radical removal rate, ABTS+ radical removal rate, and hydroxyl radical removal rate of the bionylon fibers are all at relatively high levels, and the tensile strength and elongation at break of the bionylon fibers are good, and the antibacterial effect is good. At the same time, in plant extracts... This method effectively avoids the problem of antioxidant active components affecting subsequent dyeing, resulting in a high dyeing rate for bio-nylon fibers, a slightly longer half-dyeing time compared to conventional nylon fibers, good color difference after dyeing, uniform dyeing, and high fastness to soap washing. It also effectively avoids the problem of reduced stability and deactivation of antioxidant active components during the acid dyeing process, resulting in little difference in DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, and antibacterial performance of the dyed fibers compared to before dyeing. Furthermore, it effectively improves the wash resistance of bio-nylon fibers, maintaining good antioxidant and antibacterial performance even after 20 washes.

[0079] As can be seen from Comparative Example 1, when the buckwheat leaf extract component is omitted and the silane coupling agent KH-550 is used instead of the bisaminosilane coupling agent A-2120, the amination effect of the porous base carrier decreases, affecting the sulfhydryl modification effect during the subsequent modification treatment, reducing the binding effect between the modified carrier and the antioxidant active component, and not only reducing the stability of the antioxidant active component in the nylon fiber, but also affecting the compatibility and binding performance between the composite active component and nylon. Specifically, the DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, and antibacterial performance of the fiber are clearly reduced, and the antioxidant performance and antibacterial performance decrease after 20 washes.

[0080] As can be seen from Comparative Example 2, using 3A zeolite powder instead of a porous base carrier reduces the stability of the bond between the carrier and the antioxidant active component. After omitting the amination step, the subsequent modification treatment effect is not ideal, and the binding effect between the modified carrier and the antioxidant active component cannot be effectively ensured. This reduces the stability of the antioxidant active component in nylon fibers, and the compatibility and binding performance of the composite active component containing the antioxidant active component with nylon decreases. This makes the antioxidant active component more susceptible to loss and deactivation during the preparation of nylon fibers and the subsequent fiber dyeing process, reducing the washability of the nylon fibers and decreasing their long-term antioxidant and antibacterial performance. Specifically, the DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, and antibacterial performance of the fibers decrease. The antioxidant and antibacterial performance of the dyed fibers clearly decreases, and the antioxidant and antibacterial performance decreases after 20 washes.

[0081] As can be seen from Comparative Example 3, omitting cerium nitrate hexahydrate in the preparation step of the porous base carrier prevents further improvement of the active site in the prepared porous base carrier through the synergistic coordination effect of the Zn / Ce bimetallic active center. Subsequently, the stability of binding with the antioxidant active component decreases. At the same time, omitting the modification treatment prevents further improvement of the binding stability and durability of the carrier and the antioxidant active component. Subsequently, the stability of the function of the prepared nylon fiber decreases. The antioxidant active component is more easily lost or deactivated during the preparation of the nylon fiber and the subsequent fiber dyeing process. This reduces the wash resistance of the nylon fiber and the long-term antioxidant and antibacterial performance. Specifically, the DPPH radical removal rate, ABTS+ radical removal rate, hydroxyl radical removal rate, and antibacterial performance of the fiber are clearly reduced. Fiber dyeing performance decreases, the antioxidant and antibacterial performance of the fiber after dyeing decreases, and the antioxidant and antibacterial performance of the fiber decreases after 20 washes.

[0082] Unless otherwise specified, all percentages used in this invention are mass percentages.

[0083] Finally, the above are merely preferred embodiments of the present invention and are not intended to limit the invention. The invention will be described in detail with reference to the above embodiments, but those skilled in the art should note that it is still possible to modify the technical solutions described in the above embodiments or to substitute some of the technical features. Any modifications, substitutions, improvements, etc., made without departing from the spirit and principles of the invention shall all be within the scope of protection of the invention.

Claims

1. A method for preparing bionylon fibers containing antioxidant active ingredients, comprising the steps of preparing buckwheat leaf extract, preparing Itran extract, preparing a porous base carrier, amination treatment, modification treatment, loading, preparation of a functional masterbatch, and spinning. The step of preparing the buckwheat leaf extract involves freezing and grinding the buckwheat leaves, then ultrasonically extracting and concentrating them to prepare the buckwheat leaf extract. The step of preparing the Itran extract involves freezing and crushing the stems and leaves of Itran, then ultrasonically extracting and concentrating them to prepare the Itran extract. The steps for preparing the porous base carrier are as follows: 2-methylimidazole is added to anhydrous methanol and uniformly dispersed to prepare a first solution; zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to anhydrous methanol and uniformly dispersed to prepare a second liquid; the second liquid is added to the first liquid under stirring conditions; the mixture is stirred at room temperature, then allowed to stand to obtain a reaction solution; the mixture is separated to obtain a solid; the solid is washed and dried to prepare the porous base carrier. The amination treatment step involves adding a porous base carrier to an ethanol solution, dispersing it uniformly, stirring to raise the temperature to 40-45°C, maintaining the temperature while stirring, adding bisaminosilane coupling agent A-2120 dropwise, and after the dropwise addition is complete, continuing to maintain the temperature while stirring, separating to obtain a solid, washing and drying the solid to prepare the amination carrier. The aforementioned modification treatment steps involve adding hexanedioil chloride to tetrahydrofuran, dispersing it uniformly, adding the amination support under a nitrogen atmosphere while stirring, stirring at room temperature for 10-12 hours, separating to obtain a solid, washing the solid, filtering it, adding it to N,N-dimethylformamide, adding 1,2-ethyl disulfide and triethylamine under a nitrogen atmosphere while stirring, stirring at room temperature for 5-6 hours, separating to obtain a solid, washing and drying the solid to prepare the modified support. The aforementioned loading step involves uniformly mixing buckwheat leaf extract and Itran extract to prepare a loading solution, adding the modified carrier to the loading solution, dispersing it uniformly, stirring, raising the temperature to 35-40°C, maintaining the temperature while stirring, separating to obtain a solid, washing and drying the solid to prepare a complex active ingredient. A method for preparing bionylon fibers containing antioxidant active ingredients, characterized in that the step of preparing the functional masterbatch is to prepare a functional masterbatch using a complex active ingredient.

2. In the step of preparing the porous base carrier, the time for adding the second liquid to the first liquid and stirring at room temperature is 50 to 60 minutes, and the standing time is 20 to 30 minutes. A method for preparing bionylon fibers containing an antioxidant active component as described in claim 1, characterized in that the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate is 2.2 to 2.3: 0.7 to 0.8: 0.35 to 0.

4.

3. In the amination treatment described above, the volume concentration of the ethanol solution is 75-80%. The dropping time of the bisaminosilane coupling agent A-2120 was controlled to 40-50 mins. The incubation and stirring time after the dropwise addition of bisaminosilane coupling agent A-2120 is 5 to 6 hours. A method for preparing bionylon fibers containing an antioxidant active component, as described in claim 1, characterized in that the weight ratio of the porous base carrier, the ethanol solution, and the bisaminosilane coupling agent A-2120 is 1:6 to 7:0.16 to 0.

19.

4. In the aforementioned modification treatment, the weight ratio of hexanedioil chloride, amination carrier, 1,2-ethyl disulfide, and triethylamine is 4-4.2:25-26:0.5-0.55:0.9-0.

95. The weight ratio of the amination support to the tetrahydrofuran is 1:8 to 9. A method for preparing bionylon fibers containing an antioxidant active component according to claim 1, characterized in that the weight ratio of the amination carrier to N,N-dimethylformamide is 1:4 to 5.

5. In the aforementioned loading process, the heating and stirring time after raising the temperature to 35-40°C is 5-6 hours. The volume ratio of buckwheat leaf extract to Siberian extract is 1:

1. A method for preparing bionylon fibers containing an antioxidant active component according to claim 1, characterized in that the weight ratio of the modified carrier to the support liquid is 1:6 to 6.

5.

6. The steps for preparing the buckwheat leaf extract involve freezing and grinding buckwheat leaves to obtain buckwheat leaf powder with a particle size of 1700-1800 mesh, adding the buckwheat leaf powder to an ethanol solution 10-12 times its weight, performing a first ultrasonic extraction, filtering to obtain a first extract, adding the filtration residue to an ethanol solution 8-10 times its weight, performing a second ultrasonic extraction, filtering to obtain a second extract, mixing the first and second extracts, and then vacuum concentrating them to 42-45% of their original volume to prepare the buckwheat leaf extract. The method for preparing bionylon fibers containing antioxidant active components according to claim 1, characterized in that the steps for preparing the Itran extract include freezing the stems and leaves of Itran, crushing them to obtain Itran powder with a particle size of 1700 to 1800 mesh, adding the Itran powder to an ethanol solution 13 to 15 times its weight, performing a first ultrasonic extraction, filtering to obtain a first extract, adding the filtration residue to an ethanol solution 10 to 12 times its weight, performing a second ultrasonic extraction, filtering to obtain a second extract, mixing the first and second extracts, and then vacuum concentrating to 58 to 60% of the original volume to prepare the Itran extract.

7. In the preparation of the buckwheat leaf extract, the volume concentration of the ethanol solution used in the first and second ultrasonic extractions is 55-60%, the extraction temperature for the first and second ultrasonic extractions is 40-45°C, the ultrasonic extraction frequency is 41-43 kHz, and the ultrasonic extraction power is 200-250 W. The method for preparing bionylon fibers containing antioxidant active components according to claim 6, characterized in that, in the preparation of the itran extract, the volume concentration of the ethanol solution used in the first ultrasonic extraction and the second ultrasonic extraction is 55 to 60%, the extraction temperature for the first ultrasonic extraction and the second ultrasonic extraction is 40 to 45°C, the ultrasonic extraction frequency is 41 to 43 kHz, and the ultrasonic extraction power is 200 to 250 W.

8. The steps for preparing the functional masterbatch involve placing the complex active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate into a twin-screw extruder, raising the temperature to 260-265°C, maintaining the temperature to melt, and then extruding and granulating the mixture to prepare the functional masterbatch. A method for preparing bionylon fibers containing an antioxidant active ingredient according to claim 1, characterized in that the weight ratio of the composite active ingredient, nylon 66 slices, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate is 11-12:83-86:0.9-1.1:0.7-0.8:0.65-0.

75.

9. The spinning step involves extruding and melting nylon 66 slices and a functional masterbatch in a temperature environment of 260-265°C, spinning them, controlling the spinning speed to 1700-1850 m / min, then stretching, applying an oil, and winding to prepare bionylon fibers containing antioxidant active components. The method for preparing bionylon fibers containing an antioxidant active ingredient according to claim 1, characterized in that the weight ratio of the nylon 66 slices to the functional masterbatch is 100:11 to 12.

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