Bionylon fiber containing antioxidant active ingredients and method for preparing 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 more particularly to bio-nylon fibers containing antioxidant active ingredients and a method for preparing the same. [Background technology]

[0002] Nylon fiber, known as Polyamide in English and scientifically as nylon, is the world's first synthetic fiber. Its invention dates back to the 1930s, when it was created by American chemist Carothers and his research group. Nylon fiber has exceptional abrasion resistance, ranking first among all fibers, approximately 10 times that of cotton and 20 times that of wool. Adding a small amount of nylon fiber to a blended fiber can significantly improve the abrasion resistance of the fiber. Nylon fiber also possesses good strength, elasticity, and moisture absorption. It can stretch to 103-106% and recover up to 100% of its elasticity, allowing it to withstand a certain amount of pressure and tension. This allows the garment to have a better wear and feel than polyester woven garments. Prior art studies have shown that nylon fiber is used in fields such as clothing, industrial manufacturing, and medicine. In the clothing industry, nylon fiber is widely used in the production of sportswear, outdoor wear, underwear, socks, and other items due to its abrasion resistance, strength, and good elasticity. Nylon fibers can also be blended with other fibers to create a variety of styles of clothing.In industrial production, nylon fibers' high strength and abrasion resistance make them an ideal choice for industrial textiles, and they are 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 more and more research has been conducted into improving the functionality of nylon. The new development of functional nylon fiber is of great significance to the research on the functionality of nylon fiber and the expansion of its application fields.

[0004] Tea contains antioxidant active ingredients such as tea polyphenols and catechins, orange peel contains antioxidant active ingredients such as hesperidin and naringenin, and filipendula, thuja, and grapes contain antioxidant active ingredients such as polyphenol compounds, flavonoids, and resveratrol, all of which have ideal antioxidant properties. Therefore, the prior art has already disclosed the use of plant extracts containing the above antioxidant active ingredients to improve the antioxidant functionality of nylon fibers. However, when using plant extracts to improve the antioxidant function of nylon fibers, the compatibility between the antioxidant active ingredients in the plant extract and the nylon fibers is poor. To achieve ideal dyeing results in the subsequent nylon fiber dyeing process, compatibility with the dye must be achieved in an acidic environment with a pH of 4 to 5. As a result, the stability of the antioxidant active ingredients in the plant extract is reduced and they are prone to breakdown, resulting in the desired antioxidant properties being lost, resulting in poor dyeing results, and uneven dyeing. At the same time, the antioxidant active ingredients are easily lost during the process of washing nylon fibers several times, resulting in poor washability. Furthermore, when the antioxidant function of nylon fibers is modified with plant extracts, the addition of plant extracts also affects the physical properties of the nylon fibers. Summary of the Invention

[0005] In order to solve the technical problems existing in the prior art, the present invention provides a bio-nylon fiber containing an antioxidant active ingredient, and a preparation method thereof, which can improve the binding performance of a plant extract active ingredient having antioxidant function with nylon fiber, effectively avoid the problem of the plant extract active ingredient decreasing in stability and being easily deactivated during the acid dyeing process, effectively avoid the problem of the plant extract active ingredient affecting the dyeing effect and causing uneven dyeing, and further improve the washing resistance and physical properties of nylon fiber.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] 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, preparation of a 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 for 22 to 24 hours using a low-temperature freeze dryer, and then crushed at 9000 to 10,000 rpm to obtain buckwheat leaf powder with a particle size of 1700 to 1800 mesh. The buckwheat leaf powder is then added to a 10 to 12 times weight of ethanol solution (volume concentration 55 to 60%), subjected to a first ultrasonic extraction for 15 to 20 minutes, and filtered to obtain a first extract. The filtration residue is added to an 8 to 10 times weight of ethanol solution (volume concentration 55 to 60%), subjected to a second ultrasonic extraction for 10 to 15 minutes, and filtered to obtain a second extract. The first and second extracts are then mixed and concentrated to 42 to 45% of their original volume at 62 to 65°C under a vacuum of 0.06 to 0.07 MPa.

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

[0010] Buckwheat (Fagopyrum esculentum Moench), also known as oat or ryegrass, is a dicotyledonous annual herbaceous plant of the Liao genus that prefers cool environments and tolerates poor soil. Buckwheat leaves are rich in flavonoids (rutin, quercetin, etc.), natural antioxidant active ingredients, and have excellent antioxidant properties. The flavonoid content in buckwheat leaves is higher than that in buckwheat seeds. At the same time, buckwheat leaves also have heat-reducing, antibacterial, and anti-inflammatory effects.

[0011] The steps for preparing the filipendula extract are as follows: the clean stems and leaves of filipendula are left to freeze at -40°C to -35°C for 42 to 48 hours, then frozen for 22 to 24 hours using a low-temperature freeze dryer, and then crushed at 9000 to 10000 rpm to obtain filipendula powder with a particle size of 1700 to 1800 mesh. The filipendula powder is then added to a 13 to 15 times weight of ethanol solution (volume concentration 55 to 60%) and sieved for 1 hour. The first ultrasonic extraction is carried out for 5 to 20 minutes, and then filtered to obtain the first extract. The filter residue is then added to 10 to 12 times its weight of ethanol solution (volume concentration 55 to 60%), and the second ultrasonic extraction is carried out for 10 to 15 minutes, and then filtered to obtain the second extract. The first and second extracts are then mixed and concentrated to 58 to 60% of the original volume at 62 to 65°C under a vacuum of 0.06 to 0.07 MPa to prepare the Philippendula extract.

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

[0013] Yucca smalliana Fern, also known as soft-leaf filipendra, hemp filipendra, or imported pineapple, is a plant of the Asparagaceae family, genus Yucca. The antioxidant active components in the stems and leaves of filipendra mainly include flavonoids, polyphenols, and saponins, which can exert excellent antioxidant properties through different mechanisms. At the same time, filipendra 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 to 20 times its weight of anhydrous methanol and stirred to dissolve, thereby preparing a first solution; zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 22 to 24 times its weight of anhydrous methanol and stirred to dissolve, thereby preparing a second liquid; the second liquid is added to the first liquid under stirring conditions, stirred at room temperature for 50 to 60 minutes, and then allowed to stand for 20 to 30 minutes to obtain a reaction liquid; the mixture is centrifuged at 11,000 to 12,000 rpm to obtain a solid; the solid is washed with 2 to 2.5 times its weight of anhydrous methanol, placed in a vacuum drying box, dried at 65 to 70°C under a vacuum of 0.085 to 0.095 MPa to a constant weight, and then uniformly polished to obtain a porous base carrier.

[0015] In preparing the porous base support, 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 step involves adding the porous base carrier to a 6-7 times weight amount of ethanol solution (volume concentration 75-80%), ultrasonically dispersing for 5-10 minutes, stirring, raising the temperature to 40-45°C, and stirring for 10-15 minutes. After that, bisaminosilane coupling agent A-2120 is added dropwise while stirring, and the addition time of bisaminosilane coupling agent A-2120 is controlled to 40-50 minutes. After the addition is completed, the mixture is stirred and stirred for 5-6 hours. After that, the mixture is centrifuged at 11,000-12,000 rpm to obtain a solid. The solid is washed with 2.5-3 times the weight amount of deionized water, placed in a vacuum drying box, and dried at 90-95°C under a vacuum of 0.085-0.095 MPa until a constant weight is obtained. The solid is then uniformly polished to obtain the aminated carrier.

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

[0018] The modification step involves adding hexanedioyl chloride to a reactor containing tetrahydrofuran, stirring to dissolve, then purging the air in the reactor with nitrogen, adding the aminated support while stirring, and stirring at room temperature for 10-12 hours, followed by centrifugation at 11,000-12,000 rpm to obtain a solid. The solid is then washed with 1.5-1.8 times its weight of tetrahydrofuran, filtered, and then introduced into a reactor containing N,N-dimethylformamide. The air in the reactor is then purged with nitrogen, and 1,2-ethyldisulfide and triethylamine are added while stirring, followed by stirring at room temperature for 5-6 hours, followed by centrifugation at 11,000-12,000 rpm to obtain a solid. The solid is then washed 2-3 times with 3-3.5 times its weight of deionized water, and then placed in a vacuum drying box, dried at 110-120°C under a vacuum of 0.085-0.095 MPa to a constant weight, and then uniformly polished to obtain a modified support.

[0019] In the modification treatment, the weight ratio of hexanedioyl chloride, aminated 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 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 loading step is to uniformly mix equal volumes of buckwheat leaf extract and Philippendula extract to prepare a loading solution, then add the modified carrier to the loading solution, ultrasonically disperse for 10-20 minutes, stir and heat to 35-40°C, keep warm and stir for 5-6 hours, then centrifuge at 11,000-12,000 rpm to obtain a solid, wash the solid with 3-3.5 times its weight of deionized water, put it in a vacuum drying box, dry it at 80-85°C under a vacuum of 0.04-0.05 MPa to a constant weight, and grind it uniformly to prepare the composite active ingredient.

[0021] In the loading step, the weight ratio of the modified carrier to the loading liquid is 1:6 to 6.5; The method for preparing the functional masterbatch is to charge the composite active ingredient, nylon 66 slice, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate into a twin-screw extruder, heat the mixture to 260-265°C, keep the mixture at this temperature for 25-35 minutes to melt it, and then extrude and granulate the mixture to prepare the functional masterbatch.

[0022] In preparing the functional masterbatch, the weight ratio of the composite active ingredient, nylon 66 slice, 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 involves feeding nylon 66 slices and functional masterbatch into a spinning melting device, extruding and melting them in a temperature environment of 260-265°C, and then spinning them using a screw spinning machine at a spinning speed of 1700-1850 m / min. The resulting fiber is then drawn, oiled, and wound up to produce bio-nylon fiber containing antioxidant active ingredients.

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

[0025] The bio-nylon fiber containing antioxidant active ingredients is prepared by the above-mentioned preparation method. [Effects of the Invention]

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

[0027] (1) The method for preparing bio-nylon fiber containing antioxidant active ingredients of the present invention takes into consideration the characteristics of nylon fiber and the characteristics of the antioxidant active ingredients in buckwheat leaves and Phillipendula. In each step of preparing a porous base carrier, a Zn / Ce bimetallic component is combined with the organic ligand 2-methylimidazole to improve the active sites in the prepared porous base carrier through the synergistic coordination action of the Zn / Ce bimetallic active center, thereby improving the binding stability with the subsequent antioxidant active ingredient. In the subsequent 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 ingredient, and improving the stability of the antioxidant active ingredient in the nylon fiber, while also improving the compatibility and binding performance of the composite active ingredient containing the antioxidant active ingredient with nylon. In the subsequent modification step, the aminated carrier is subjected to sulfhydryl modification treatment. The modified carrier is then subjected to a process to further improve the bonding stability and durability of the antioxidant active ingredient with the modified carrier, thereby further improving its functional stability in nylon fiber. In the subsequent loading step, buckwheat leaf extract and filipendula extract, which contain antioxidant active ingredients such as flavonoids and polyphenols, are selected. The buckwheat leaf extract and filipendula extract are mixed to form a loading solution, which is then subjected to an adsorption and bonding loading process using the modified carrier to prepare a composite active ingredient. The composite active ingredient is then used to prepare a functional masterbatch, which is then combined with nylon raw materials and spun into fiber to prepare bio-nylon fiber containing the antioxidant active ingredient. As a result, the bonding performance of the plant extract active ingredient with antioxidant function and nylon fiber is improved, effectively avoiding the problem of the antioxidant active ingredient being unstable and easily deactivated during acid dyeing, and effectively avoiding the problem of the antioxidant active ingredient affecting the dyeing effect and causing uneven dyeing, and further improving the washing resistance and physical properties of the bio-nylon fiber.

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

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

[0030] (4) The bio-nylon fiber containing the antioxidant active ingredient of the present invention has a dyeing rate of 97.1 to 97.3%, a half-dyeing time extension rate of 3.8 to 4.0%, a dyeing color difference value ΔE of 0.03 to 0.04, and a soap fastness of grade 4.

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

[0032] (6) After 20 washes, the bio-nylon fiber containing the antioxidant active ingredient of the present invention has a DPPH radical scavenging rate of 83.0-83.6%, an ABTS+ radical scavenging rate of 81.4-81.9%, a hydroxyl radical scavenging 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%. DETAILED DESCRIPTION OF THE INVENTION

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

[0034] Example 1 This example provides a method for preparing bio-nylon fiber containing antioxidant active ingredients, specifically as follows: 1. Preparation of buckwheat leaf extract Clean buckwheat leaves were frozen at -40°C for 42 hours, then frozen for 22 hours in a low-temperature freeze dryer, and then crushed at 9000 rpm to obtain buckwheat leaf powder with a particle size of 1700 mesh. The buckwheat leaf powder was then added to a 10-fold weight of ethanol solution (volume concentration 55%) and subjected to a first ultrasonic extraction for 15 minutes. The resulting mixture was filtered to obtain the first extract. The residue was then added to an 8-fold weight of ethanol solution (volume concentration 55%) and subjected to a second ultrasonic extraction for 10 minutes. The second extract was then filtered to obtain the second extract. The first and second extracts were then mixed and concentrated to 42% of their original volume at 62°C under a vacuum of 0.06 MPa to obtain the buckwheat leaf extract. Here, the ultrasonic extraction temperature is controlled at 40°C, the ultrasonic extraction frequency is 41kHz, and the ultrasonic extraction power is 200W.

[0035] 2. Preparation of Philipendula extract Clean Filipendula stems and leaves were frozen at -40°C for 42 hours, then frozen for 22 hours using a low-temperature freeze dryer, and then crushed at 9000 rpm to obtain Filipendula powder with a particle size of 1700 mesh. The Filipendula powder was then added to a 13-fold weight of ethanol solution (volume concentration 55%) and subjected to the first ultrasonic extraction for 15 minutes. The filtered residue was then added to a 10-fold weight of ethanol solution (volume concentration 55%) and subjected to the second ultrasonic extraction for 10 minutes. The filtered residue was then mixed and concentrated to 58% of the original volume at 62°C under a vacuum of 0.06 MPa to obtain Filipendula extract. Here, the ultrasonic extraction temperature is controlled at 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 of anhydrous methanol and stirred to dissolve, preparing a first solution; zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 22 times its weight of anhydrous methanol and stirred to dissolve, preparing a second liquid; under stirring conditions, the second liquid is added to the first liquid, stirred at room temperature for 50 minutes, and then allowed to stand for 20 minutes to obtain a reaction liquid; the mixture is centrifuged at 11,000 rpm to obtain a solid; the solid is washed with twice its weight of anhydrous methanol, then placed in a vacuum drying box and dried at 65°C under a vacuum of 0.085 MPa to a constant weight; and then uniformly polished to obtain a porous base carrier. Here, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate was 2.2:0.7:0.35.

[0037] 4. Amination treatment The porous base carrier is placed in a 6-fold weight amount of ethanol solution (volume concentration 75%) and ultrasonically dispersed for 5 minutes. After stirring, the temperature is raised to 40°C and the mixture is kept warm and stirred for 10 minutes. Then, while stirring, the bisaminosilane coupling agent A-2120 is added dropwise. The addition time of the bisaminosilane coupling agent A-2120 is controlled to 40 minutes. After the addition is completed, the mixture is kept warm and stirred for 5 hours. Then, the mixture is centrifuged at 11,000 rpm to obtain a solid. The solid is washed with 2.5 times its weight amount of deionized water and placed in a vacuum drying box. It is dried at 90°C under a vacuum of 0.085 MPa to a constant weight and then uniformly polished to obtain the aminated carrier. Here, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 was 1:0.16.

[0038] 5. Modification processing Hexanediol chloride is added to a reactor containing tetrahydrofuran, stirred to dissolve, and then the air in the reactor is replaced with nitrogen. The aminated carrier is added while stirring, and after stirring at room temperature for 10 hours, centrifuged at 11,000 rpm to obtain a solid. The solid is washed with 1.5 times its weight of tetrahydrofuran, filtered, and then added to a reactor containing N,N-dimethylformamide. The air in the reactor is replaced with nitrogen. 1,2-ethyldisulfide and triethylamine are added while stirring, and after stirring at room temperature for 5 hours, centrifuged at 11,000 rpm to obtain a solid. The solid is washed three times with three times its weight of deionized water, and then placed in a vacuum drying box, dried at 110 ° C under a vacuum of 0.085 MPa to a constant weight, and then uniformly polished to obtain a modified carrier. Here, the weight ratio of hexanedioyl chloride, aminated carrier, 1,2-ethyl disulfide, and triethylamine was 4:25:0.5:0.9. The weight ratio of the aminated carrier to tetrahydrofuran is 1:8. The weight ratio of the aminated carrier to N,N-dimethylformamide was 1:4.

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

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

[0041] 8. Spinning Nylon 66 slices and functional master batches are placed in a spinning melting device and extruded to melt them in a temperature environment of 260°C. After that, they are spun using a screw spinning machine, and the spinning speed is controlled to 1700 m / min. After that, they are stretched, oiled, and wound up to prepare bio-nylon fibers containing antioxidant active ingredients. Here, the weight ratio of nylon 66 slice to functional masterbatch was 100:11.

[0042] This example further provides a bio-nylon fiber containing antioxidant active ingredients, prepared by the above preparation method.

[0043] <Example 2> This example provides a method for preparing bio-nylon fiber containing antioxidant active ingredients, specifically as follows: 1. Preparation of buckwheat leaf extract Clean buckwheat leaves were frozen at -38°C for 45 hours, then frozen for 23 hours in a low-temperature freeze dryer, and crushed at 9,500 rpm to obtain buckwheat leaf powder with a particle size of 1,750 mesh. The buckwheat leaf powder was then added to an 11-fold weight of ethanol solution (volume concentration 57%) and subjected to the first ultrasonic extraction for 18 minutes. The resulting mixture was filtered to obtain the first extract. The residue was then added to a 9-fold weight of ethanol solution (volume concentration 57%) and subjected to the second ultrasonic extraction for 12 minutes. The second extract was then filtered to obtain the second extract. The first and second extracts were then mixed and concentrated to 43% of their original volume at 63°C under a vacuum of 0.065 MPa to obtain the buckwheat leaf extract. Here, the ultrasonic extraction temperature is controlled at 42°C, the ultrasonic extraction frequency is 42kHz, and the ultrasonic extraction power is 240W.

[0044] 2. Preparation of Philipendula extract The clean stems and leaves of Philipendula were frozen at -38°C for 45 hours, then frozen for 23 hours using a low-temperature freeze dryer, and then crushed at 9500 rpm to obtain Philipendula powder with a particle size of 1750 mesh. The Philipendula powder was then added to a 14-fold weight ethanol solution (volume concentration 57%) and subjected to the first ultrasonic extraction for 18 minutes. The filtered residue was then added to an 11-fold weight ethanol solution (volume concentration 57%) and subjected to the second ultrasonic extraction for 12 minutes. The filtered residue was then mixed and concentrated to 59% of the original volume at 63°C under a vacuum of 0.065 MPa to obtain Philipendula extract. Here, the ultrasonic extraction temperature is controlled at 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 of anhydrous methanol and stirred to dissolve, preparing a first solution; zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 23 times its weight of anhydrous methanol and stirred to dissolve, preparing a second liquid; under stirring conditions, the second liquid is added to the first liquid, stirred at room temperature for 55 minutes, and then allowed to stand for 25 minutes to obtain a reaction liquid; the mixture is centrifuged at 11,500 rpm to obtain a solid; the solid is washed with 2.3 times its weight of anhydrous methanol, then placed in a vacuum drying box and dried at 68°C under a vacuum of 0.09 MPa to a constant weight, and then uniformly polished to obtain a porous base carrier. Here, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate was 2.25:0.75:0.38.

[0046] 4. Amination treatment The porous base carrier was placed in 6.5 times its weight of ethanol solution (volume concentration 78%) and ultrasonically dispersed for 8 minutes. After stirring, the temperature was raised to 42°C and the mixture was stirred for 12 minutes. After that, the bisaminosilane coupling agent A-2120 was added dropwise while stirring. The addition time of the bisaminosilane coupling agent A-2120 was controlled to 45 minutes. After the addition was completed, the mixture was stirred and kept warm for 5.5 hours. After that, the mixture was centrifuged at 11,500 rpm to obtain a solid. The solid was washed with 2.8 times its weight of deionized water and then placed in a vacuum drying box. It was dried at 92°C under a vacuum of 0.09 MPa until a constant weight was obtained, and then uniformly polished to obtain the aminated carrier. Here, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 was 1:0.18.

[0047] 5. Modification processing Hexanediol chloride is added to a reactor containing tetrahydrofuran, stirred and dissolved, and the air in the reactor is replaced with nitrogen. The aminated carrier is added while stirring, and after stirring at room temperature for 11 hours, centrifuged at 11,500 rpm to obtain a solid. The solid is washed with 1.6 times its weight of tetrahydrofuran, filtered, and then added to a reactor containing N,N-dimethylformamide. The air in the reactor is replaced with nitrogen. 1,2-ethyldisulfide and triethylamine are added while stirring, and after stirring at room temperature for 5.5 hours, centrifuged at 11,500 rpm to obtain a solid. The solid is washed three times with 3.2 times its weight of deionized water, and then placed in a vacuum drying box. It is dried at 115 ° C under a vacuum of 0.09 MPa to a constant weight, and then uniformly polished to obtain a modified carrier. Here, the weight ratio of hexanedioyl chloride, aminated carrier, 1,2-ethyl disulfide, and triethylamine was 4.1:25.5:0.53:0.92. The weight ratio of the aminated carrier to tetrahydrofuran is 1:8.5. The weight ratio of the aminated carrier to N,N-dimethylformamide was 1:4.5.

[0048] 6. Carrying Equal volumes of buckwheat leaf extract and Philippendula extract are mixed uniformly to prepare a carrier solution. The modified carrier is then added to the carrier solution and ultrasonically dispersed for 15 minutes. The mixture is then stirred and heated to 38°C. After 5.5 hours of warm stirring, the mixture is centrifuged at 11,500 rpm to obtain a solid. The solid is then washed with 3.2 times its weight of deionized water, placed in a vacuum drying box, dried at 83°C under a vacuum of 0.045 MPa to a constant weight, and then uniformly polished to prepare the composite active ingredient. Here, the weight ratio of the modified carrier to the carrier liquid is 1:6.3.

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

[0050] 8. Spinning Nylon 66 slices and functional master batches are placed in a spinning melting device and extruded to melt them in a temperature environment of 263°C. After that, they are spun using a screw spinning machine, and the spinning speed is controlled to 1800 m / min. After that, they are stretched, oiled, and wound up to prepare bio-nylon fibers containing antioxidant active ingredients. Here, the weight ratio of nylon 66 slice to functional masterbatch was 100:11.7.

[0051] This example further provides a bio-nylon fiber containing antioxidant active ingredients, prepared by the above preparation method.

[0052] Example 3 This example provides a method for preparing bio-nylon fiber containing antioxidant active ingredients, specifically as follows: 1. Preparation of buckwheat leaf extract Clean buckwheat leaves were frozen at -35°C for 48 hours, then frozen for 24 hours in a low-temperature freeze dryer, and crushed at 10,000 rpm to obtain buckwheat leaf powder with a particle size of 1800 mesh. The buckwheat leaf powder was then added to a 12-fold weight ethanol solution (60% volumetric concentration) and subjected to a first ultrasonic extraction for 20 minutes. The resulting mixture was filtered to obtain the first extract. The residue was then added to a 10-fold weight ethanol solution (60% volumetric concentration) and subjected to a second ultrasonic extraction for 15 minutes. The second extract was then filtered to obtain the second extract. The first and second extracts were then mixed and concentrated to 45% of their original volume at 65°C under a vacuum of 0.07 MPa to obtain the buckwheat leaf extract. Here, the ultrasonic extraction temperature is controlled at 45°C, the ultrasonic extraction frequency is 43kHz, and the ultrasonic extraction power is 250W.

[0053] 2. Preparation of Philipendula extract Clean Filipendula stems and leaves are frozen at -35°C for 48 hours, then frozen for 24 hours using a low-temperature freeze dryer, and then crushed at 10,000 rpm to obtain Filipendula powder with a particle size of 1800 mesh. The Filipendula powder is then added to a 15-fold weight of ethanol solution (volume concentration 60%) and subjected to a first ultrasonic extraction for 20 minutes. The filtered residue is then added to a 12-fold weight of ethanol solution (volume concentration 60%) and subjected to a second ultrasonic extraction for 15 minutes. The filtered residue is then filtered to obtain a second extract. The first and second extracts are mixed and then concentrated to 60% of their original volume at 65°C under a vacuum of 0.07 MPa to prepare Filipendula extract. Here, the ultrasonic extraction temperature is controlled at 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 of anhydrous methanol and stirred to dissolve, preparing a first solution; zinc nitrate hexahydrate and cerium nitrate hexahydrate are added to 24 times its weight of anhydrous methanol and stirred to dissolve, preparing a second liquid; the second liquid is added to the first liquid under stirring conditions, stirred at room temperature for 60 minutes, and then allowed to stand for 30 minutes to obtain a reaction liquid; the mixture is centrifuged at 12,000 rpm to obtain a solid; the solid is washed with 2.5 times its weight of anhydrous methanol, placed in a vacuum drying box, dried at 70°C under a vacuum of 0.095 MPa to a constant weight, and then uniformly polished to obtain a porous base carrier. Here, the molar ratio of 2-methylimidazole, zinc nitrate hexahydrate, and cerium nitrate hexahydrate was 2.3:0.8:0.4.

[0055] 4. Amination treatment The porous base carrier is placed in a 7-fold weight amount of ethanol solution (volume concentration 80%) and ultrasonically dispersed for 10 minutes. After stirring, the temperature is raised to 45°C and the mixture is kept warm and stirred for 15 minutes. Then, while stirring, the bisaminosilane coupling agent A-2120 is added dropwise. The addition time of the bisaminosilane coupling agent A-2120 is controlled to 50 minutes. After the addition is completed, the mixture is kept warm and stirred for 6 hours. Then, the mixture is centrifuged at 12,000 rpm to obtain a solid. The solid is washed with 3-fold weight amount of deionized water and then placed in a vacuum drying box. It is dried at 95°C under a vacuum of 0.095 MPa until a constant weight is obtained, and then uniformly polished to obtain the aminated carrier. Here, the weight ratio of the porous base carrier to the bisaminosilane coupling agent A-2120 was 1:0.19.

[0056] 5. Modification processing Hexanediol chloride is added to a reactor containing tetrahydrofuran, stirred and dissolved, and the air in the reactor is replaced with nitrogen. The aminated carrier is added while stirring, and after stirring at room temperature for 12 hours, centrifuged at 12,000 rpm to obtain a solid. The solid is washed with 1.8 times its weight of tetrahydrofuran, filtered, and then added to a reactor containing N,N-dimethylformamide. The air in the reactor is replaced with nitrogen. 1,2-ethyldisulfide and triethylamine are added while stirring, and after stirring at room temperature for 6 hours, centrifuged at 12,000 rpm to obtain a solid. The solid is washed three times with 3.5 times its weight of deionized water, and then placed in a vacuum drying box. It is dried at 120 ° C under a vacuum of 0.095 MPa to a constant weight, and then uniformly polished to obtain a modified carrier. Here, the weight ratio of hexanedioyl chloride, aminated carrier, 1,2-ethyl disulfide, and triethylamine was 4.2:26:0.55:0.95. The weight ratio of the aminated carrier to tetrahydrofuran is 1:9. The weight ratio of the aminated carrier to N,N-dimethylformamide was 1:5.

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

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

[0059] 8. Spinning Nylon 66 slices and functional master batches are placed in a spinning melting device and extruded to melt them in a temperature environment of 265°C. After that, they are spun using a screw spinning machine, and the spinning speed is controlled to 1850 m / min. After that, they are stretched, oiled, and wound up to prepare bio-nylon fibers containing antioxidant active ingredients. Here, the weight ratio of nylon 66 slice to functional masterbatch was 100:12.

[0060] This example further provides a bio-nylon fiber containing antioxidant active ingredients, prepared by the above preparation method. <Comparative Example 1> The technical solution of Example 2 is adopted, with the following differences: 1) the step of preparing buckwheat leaf extract is omitted, and in the subsequent loading step, Phillipendula extract is used as the loading liquid; 2) in the amination treatment step, silane coupling agent KH-550 is used instead of bisaminosilane coupling agent A-2120.

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

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

[0063] The antioxidant and physical properties of the nylon fibers of Examples 1 to 3 and Comparative Examples 1 to 3 were determined, respectively. Specifically, the DPPH· radical scavenging rate, ABTS+· radical scavenging rate, hydroxyl radical scavenging rate, breaking strength, and breaking elongation of each nylon fiber were determined.

[0064] Specifically, the DPPH radical scavenging rate was determined as follows: 2.5 mg of 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH) was weighed out and dissolved in an appropriate amount of absolute ethanol. Shake well away from light to completely dissolve the solution, then add absolute ethanol to a final volume of 100 mL to prepare a 25 mg / L DPPH ethanol solution.

[0065] 2.0 g of nylon fiber from each of Examples 1 to 3 and Comparative Examples 1 to 3 was weighed and placed in an ultrasonic extraction bottle containing 50 mL of ethanol solution (volume concentration 60%). After immersion for 16 hours, the fiber was subjected to ultrasonic extraction for 10 minutes. The filtrate was then collected by filtration using a Büchner funnel and transferred to a rotary evaporator. The rotary evaporation temperature was controlled to 55°C and the rotary evaporation vacuum was 0.085 MPa. When the filtrate was evaporated to 2 mL, the rotary evaporation was stopped and the ethanol solution (volume concentration 60%) 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 evenly, and leave to stand for 10 minutes away from light. Then, measure the absorbance at a wavelength of 517 nm using a spectrophotometer to calculate the DPPH radical scavenging rate.

[0067] The ABTS+· radical scavenging rate was determined as follows: 200.0 mg of 2,2-biazobis(3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt ABTS and 34.4 mg of potassium persulfate were weighed and dissolved in 50.0 mL of deionized water. The solution was left at room temperature for 24 hours away from light to obtain the ABTS mother solution. An appropriate amount of the ABTS mother solution was then diluted with 95% ethanol by volume until the absorbance at 734 nm reached 0.70, to obtain the diluted ABTS solution.

[0068] The test solution was prepared in the same manner as in the test solution preparation for the DPPH radical scavenging rate detection.

[0069] Add 0.5 mL of the test solution to 5 mL of ABTS diluted solution, mix evenly, and leave to stand for 10 minutes away from light. Then, measure the absorbance at a wavelength of 734 nm using a spectrophotometer to calculate the ABTS+· radical scavenging rate.

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

[0071] For specific methods of detecting breaking strength and breaking elongation, please refer to the national standard GB / T14344-2022 "Test method for tensile properties of chemical fiber filaments." The specific results are shown in the table below: JPEG2026042681000001.jpg53170

[0072] Furthermore, the antibacterial properties of the nylon fibers of Examples 1 to 3 and Comparative Examples 1 to 3 were determined, and the specific methods can be found in GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles, Part 3: Vibration method."

[0073] The bacterial species used to detect antibacterial activity are Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 8739), and Candida albicans (ATCC 10231). The specific results are shown in the table below: JPEG2026042681000002.jpg67170

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

[0075] The half-dyeing time extension rate is calculated as follows: [(half-dyeing time after nylon fiber modification with antioxidant active ingredient - reference value) / reference value] x 100%. The specific results are shown in the table below: JPEG2026042681000003.jpg64170

[0076] Furthermore, the DPPH radical scavenging rate, ABTS+ radical scavenging rate, hydroxyl radical scavenging rate, and antibacterial performance of the nylon fibers of Examples 1 to 3 and Comparative Examples 1 to 3 after dyeing were measured, and the specific results are shown in the table below: JPEG2026042681000004.jpg131170

[0077] Furthermore, each of the nylon fibers of Examples 1 to 3 and Comparative Examples 1 to 3 was spun into a pure fabric, and then cut into 20cm x 20cm wash samples. Each wash sample was placed in a washing machine, the wash water temperature was set to 45°C, and one wash was performed for 30 minutes. After washing, the samples were air-dried at a constant temperature of 35°C. This washing-drying process was repeated 20 times, and then the DPPH radical scavenging rate, ABTS+ radical scavenging rate, hydroxyl radical scavenging rate, and antibacterial performance of each nylon fiber were measured after dyeing. The specific results are shown in the table below: JPEG2026042681000005.jpg131170

[0078] As can be seen from the above table, the method for preparing bio-nylon fiber containing antioxidant active ingredients of the present invention has the following advantages regarding the properties of nylon fiber and antioxidant active ingredient: in the step of preparing a porous base carrier, a Zn / Ce bimetallic component is combined with the organic ligand 2-methylimidazole, and the synergistic coordination effect of the Zn / Ce bimetallic active center improves the active sites in the prepared porous base carrier, thereby improving the subsequent bonding stability with the antioxidant active ingredient; in the subsequent amination step, a bisaminosilane coupling agent is used to amide the porous base carrier, effectively introducing amino groups, thereby improving the effect of the subsequent modification treatment, ensuring the bonding effect between the modified carrier and the antioxidant active ingredient, and improving the stability of the antioxidant active ingredient in the nylon fiber; and improving the compatibility and bonding performance of the composite active ingredient containing the antioxidant active ingredient with nylon; in the subsequent modification step, the aminated carrier is subjected to sulfhydryl modification treatment, which further improves the bonding stability and durability between the modified carrier and the antioxidant active ingredient, thereby further improving the functional stability in the nylon fiber; and in the subsequent loading step, Buckwheat leaf extract and filipendula extract containing antioxidant active ingredients such as lavandoids and polyphenols are selected, and the buckwheat leaf extract and filipendula extract are mixed to form a carrier solution, and then the adsorption and binding support process is carried out using a modified carrier to prepare a composite active ingredient. Subsequently, a functional masterbatch is prepared using the composite active ingredient, and then it is spun with nylon raw materials to prepare bio-nylon fiber containing antioxidant active ingredients. This effectively improves the binding performance of the composite active ingredient and the bio-nylon fiber, giving the bio-nylon fiber antioxidant and antibacterial properties, and the bio-nylon fiber is The DPPH radical scavenging rate, ABTS+ radical scavenging rate, and hydroxyl radical scavenging rate of bio-nylon fiber are all relatively high. The breaking strength and breaking elongation of bio-nylon fiber are good, and it has good antibacterial effect. At the same time, it effectively avoids the problem that the antioxidant active components in plant extracts affect subsequent dyeing. The dyeing rate of bio-nylon fiber is high, and the half-dyeing time is slightly longer than that of conventional nylon fiber. The color difference value of the dyed fiber is good, the dyeing is uniform, and the fastness to soap washing is high. The stability of the antioxidant active components is not reduced during the acid dyeing process.The problem of deactivation is effectively avoided, and the DPPH radical scavenging rate, ABTS+ radical scavenging rate, hydroxyl radical scavenging rate, and antibacterial performance of the dyed fiber are not significantly different from those before dyeing. Furthermore, the washing resistance of the bio-nylon fiber can be effectively improved, and good antioxidant and antibacterial performance can be maintained even after 20 washes.

[0079] As can be seen from Comparative Example 1, omitting the buckwheat leaf extract and substituting the silane coupling agent KH-550 for the bisaminosilane coupling agent A-2120 resulted in a reduced amination effect on the porous base carrier, which affected the sulfhydryl modification effect during subsequent modification treatment. This reduced the bonding between the modified carrier and the antioxidant active ingredient, reducing not only the stability of the antioxidant active ingredient in the nylon fiber but also its compatibility and bonding performance with the nylon. Specifically, the DPPH radical scavenging rate, ABTS+ radical scavenging rate, and hydroxyl radical scavenging rate of the fiber, as well as its antibacterial performance, were significantly reduced, and the antioxidant and antibacterial performance declined after 20 washes.

[0080] As can be seen from Comparative Example 2, using 3A zeolite powder instead of a porous base carrier reduced the stability of the bond between the carrier and the antioxidant active ingredient. After omitting the amination step, the subsequent modification treatment was less effective, failing to effectively ensure the bond between the modified carrier and the antioxidant active ingredient. This reduced the stability of the antioxidant active ingredient in the nylon fiber, reducing the compatibility and bonding performance of the antioxidant-containing composite with nylon. This led to loss and inactivation of the antioxidant active ingredient during nylon fiber preparation and subsequent fiber dyeing, resulting in reduced washability and reduced long-term antioxidant and antibacterial performance. Specifically, the DPPH radical scavenging rate, ABTS+ radical scavenging rate, and hydroxyl radical scavenging rate of the fiber, as well as reduced antibacterial performance, significantly reduced the antioxidant and antibacterial performance of the fiber after dyeing, and reduced antioxidant and antibacterial performance after 20 washes.

[0081] As can be seen from Comparative Example 3, omitting cerium nitrate hexahydrate in the preparation of the porous base carrier did not further improve the active sites in the prepared porous base carrier due to the synergistic coordination effect of the Zn / Ce bimetallic active centers, resulting in a decrease in the stability of the bond with the antioxidant active ingredient. At the same time, omitting the modification treatment did not further improve the bond stability and durability between the carrier and the antioxidant active ingredient, resulting in a decrease in the functional stability of the prepared nylon fiber. This led to the loss or inactivation of the antioxidant active ingredient during nylon fiber preparation and the subsequent dyeing process, resulting in a decrease in the washing resistance of the nylon fiber and a decrease in its long-term antioxidant and antibacterial performance. Specifically, the DPPH radical scavenging rate, ABTS+ radical scavenging rate, hydroxyl radical scavenging rate, and antibacterial performance of the fiber were significantly reduced, resulting in a decrease in fiber dyeing performance, a decrease in the antioxidant and antibacterial performance of the fiber after dyeing, and a decrease in the antioxidant and antibacterial performance of the fiber after 20 washes.

[0082] Unless otherwise specified, all percentages used in the present invention are by mass.

[0083] Finally, the above are only preferred embodiments of the present invention, and are not intended to limit the present invention. The present invention will be described in detail with reference to the above embodiments, but it should be noted that those skilled in the art can still modify the technical solutions described in the above embodiments or equivalently replace some technical features. Any modifications, equivalent replacements, improvements, etc. made without departing from the spirit and principle of the present invention shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing bio-nylon fiber containing antioxidant active ingredients, comprising the steps of preparing buckwheat leaf extract, preparing filipendula extract, preparing a porous base carrier, amination treatment, modification treatment, supporting, preparing a functional masterbatch, and spinning; The step of preparing the buckwheat leaf extract comprises freezing and crushing the buckwheat leaves, followed by ultrasonic extraction and concentration to prepare the buckwheat leaf extract; The step of preparing the filipendula extract is to freeze and crush the stems and leaves of filipendula, and then ultrasonically extract and concentrate the filipendula extract; The steps of preparing the porous base carrier include adding 2-methylimidazole to anhydrous methanol and dispersing it uniformly to prepare a first solution, adding zinc nitrate hexahydrate and cerium nitrate hexahydrate to anhydrous methanol and dispersing it uniformly to prepare a second liquid, adding the second liquid to the first liquid under stirring conditions, stirring at room temperature, and then allowing to stand to obtain a reaction liquid, which is separated to obtain a solid, which is washed and dried to prepare a porous base carrier; The amination step is as follows: the porous base carrier is introduced into an ethanol solution, uniformly dispersed, and then stirred to raise the temperature to 40-45°C, and the mixture is stirred while maintaining the temperature; the bisaminosilane coupling agent A-2120 is added dropwise; after the addition is completed, the mixture is continuously stirred while maintaining the temperature; and the solid is separated to obtain a solid product, which is then washed and dried to prepare an aminated carrier; The modification treatment steps are as follows: hexanedioyl chloride is added to tetrahydrofuran, and uniformly dispersed; under a nitrogen atmosphere, while stirring, an aminated carrier is added; stirring is continued at room temperature for 10-12 hours, and then a solid is obtained by separation; the solid is washed, filtered, and added to N,N-dimethylformamide; under a nitrogen atmosphere, while stirring, 1,2-ethyldisulfide and triethylamine are added; stirring is continued at room temperature for 5-6 hours, and then a solid is obtained by separation; the solid is washed and dried to prepare a modified carrier; The loading step is to uniformly mix the buckwheat leaf extract and the filipendula extract to prepare a loading liquid, add the modified carrier to the loading liquid, uniformly disperse it, stir and heat it to 35-40°C, keep it warm and stir, then separate it to obtain a solid, wash and dry the solid to prepare a composite active ingredient; A method for preparing bio-nylon fiber containing antioxidant active ingredients, characterized in that the step of preparing a functional masterbatch is to prepare a functional masterbatch using a composite 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 time for standing is 20 to 30 minutes; 2. The method for preparing bio-nylon fiber containing antioxidant active ingredients according to claim 1, wherein 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.

3. In the amination treatment, the volume concentration of the ethanol solution is 75 to 80%; The dropwise addition time of the bisaminosilane coupling agent A-2120 was controlled to 40 to 50 minutes. After the dropwise addition of the bisaminosilane coupling agent A-2120 is completed, the stirring time is kept at the same temperature for 5 to 6 hours.

2. The method for preparing bio-nylon fiber containing antioxidant active ingredients according to claim 1, wherein the weight ratio of the porous base carrier, the ethanol solution, and the bisaminosilane coupling agent A-2120 is 1:6-7:0.16-0.

19.

4. In the modification treatment, the weight ratio of hexanedioyl chloride, aminated carrier, 1,2-ethyl disulfide, and triethylamine is 4 to 4.2: 25 to 26: 0.5 to 0.55: 0.9 to 0.95; The weight ratio of the aminated carrier to tetrahydrofuran is 1:8-9; 2. The method for preparing bio-nylon fiber containing antioxidant active ingredients according to claim 1, wherein the weight ratio of the aminated carrier to N,N-dimethylformamide is 1:4-5.

5. In the loading, the time for stirring while keeping the temperature after raising the temperature to 35 to 40°C is 5 to 6 hours, The volume ratio of buckwheat leaf extract to filipendula extract is 1:

1. The method for preparing bio-nylon fiber containing antioxidant active ingredients according to claim 1, characterized in that the weight ratio of the modified carrier to the supporting liquid is 1:6-6.

5.

6. The steps of preparing the buckwheat leaf extract include freezing buckwheat leaves, pulverizing them to obtain buckwheat leaf powder with a particle size of 1700-1800 mesh, adding the buckwheat leaf powder to an ethanol solution with a weight ratio of 10-12 times, performing a first ultrasonic extraction, filtering to obtain a first extract, adding the filtration residue to an ethanol solution with a weight ratio of 8-10 times, performing a second ultrasonic extraction, filtering to obtain a second extract, mixing the first extract and the second extract, and then vacuum concentrating the mixture to 42-45% of the original volume to obtain the buckwheat leaf extract; The method for preparing bio-nylon fiber containing antioxidant active ingredients as described in claim 1, characterized in that the step of preparing the filipendula extract comprises freezing the stems and leaves of filipendula, crushing them to obtain filipendula powder with a particle size of 1700 to 1800 mesh, adding the filipendula powder to an ethanol solution of 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 of 10 to 12 times its weight, performing a second ultrasonic extraction, filtering to obtain a second extract, mixing the first extract and the second extract, and then vacuum concentrating to 58 to 60% of the original volume to obtain the filipendula extract.

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

8. The step of preparing the functional masterbatch is to charge the composite active ingredient, nylon 66 slice, antioxidant SEED, polyvinylpyrrolidone, and sodium stearate into a twin-screw extruder, heat the mixture to 260-265°C, keep the mixture warm to melt, and then extrude and granulate the mixture to prepare the functional masterbatch; 2. The method for preparing bio-nylon fiber containing antioxidant active ingredients according to claim 1, wherein the weight ratio of the composite active ingredient, nylon 66 slice, 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 the nylon 66 slice and the functional masterbatch in a temperature environment of 260-265°C to melt them, spinning them, controlling the spinning speed at 1700-1850m / min, and then stretching, adding oil, and winding them up to prepare a bio-nylon fiber containing antioxidant active ingredients; 2. The method for preparing bio-nylon fiber containing antioxidant active ingredients according to claim 1, wherein the weight ratio of the nylon 66 slice to the functional masterbatch is 100:11-12.

10. A bio-nylon fiber containing an antioxidant active ingredient, characterized in that it is prepared by the method for preparing a bio-nylon fiber containing an antioxidant active ingredient according to any one of claims 1 to 9.

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