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

Abstract

The invention relates to the technical field of viscose large biological fibers, in particular to a viscose large biological fiber containing antioxidant active ingredients and a preparation method of the viscose large biological fiber. The viscose large biological fiber is prepared from the following raw materials in parts by weight through reaction: 20 to 24 parts of COFs carrier, 5 to 8 parts of plant source antioxidant active component, 200 to 240 parts of spinning solution, 2 to 4 parts of lauryl sodium sulfate, 2 to 4 parts of glycerol monooleate, 3 to 5 parts of cyclodextrin, 2 to 4 parts of titanium dioxide and 3 to 5 parts of silane coupling agent. The antioxidant active component is attached to the COFs carrier, in the prepared viscose large biological fiber, the COFs carrier serves as a framework of the viscose large biological fiber, and the end of the COFs carrier is exposed out of or close to the skin of the viscose large biological fiber, so that the antioxidant active component on the COFs carrier is conveniently transferred to the skin of the viscose large biological fiber; it is guaranteed that the active components can play a role smoothly, and the anti-oxidation effect of the viscose large biological fiber is good.

Description

Technical Field

[0001] The invention relates to the technical field of viscose macro-biofibers, in particular to a viscose macro-biofiber containing antioxidant active ingredients and a preparation method thereof. Background Art

[0002] Viscose fiber, also known as viscose silk, is made of natural fibers such as wood fiber and cotton linters. After being processed through alkalization, aging, and sulfonation to make soluble cellulose xanthate, it is dissolved in dilute alkali solution to make viscose, and then the viscose is used as the spinning solution to spin through wet spinning to make regenerated cellulose fiber. Viscose fiber has the advantages of strong hygroscopicity, strong air permeability, comfortable wearing, smooth and cool, anti-static, easy to dye, good spinnability, etc., and is widely used in clothing, home textiles, non-woven fabrics and other fields.

[0003] Viscose macro-biofiber, i.e. macro-biofunctional viscose fiber, is a viscose polymer with a certain amount of functional materials that can act on the human body or other organisms added to it, and after being processed with special technology, the viscose fiber is given one or several functions. In recent years, there are many varieties of bio-functional fibers at home and abroad, and they are constantly being innovated, which provides a lot of space for the development of functional products. Its market consumption is also growing, and it has broad application prospects in the fields of construction, transportation, water conservancy, agriculture, fishery, medical and health care, and even electronics, communications, national defense, etc. Therefore, functional viscose fiber has become the development focus of the viscose fiber field in the future. Functional fiber materials have attracted the attention of the industry and the market with their particularity, differentiation, and functional targeting.

[0004] The antioxidant properties of viscose biofiber can be improved by adding antioxidant active ingredients. Among them, plant-derived antioxidant active ingredients are deeply loved by users due to their excellent environmental performance. The sources of plant-derived antioxidant active ingredients mainly include: tea, mint, lavender, tomato, orange, yucca, knotweed and grapes.

[0005] In order to improve the antioxidant properties of viscose large bio-fibers, there are mainly two modification methods in the prior art. One is to mix the active components into the spinning solution and directly spin them. The problem that may exist in this method is that when the volume of the active components is small, the active components are completely wrapped by the spinning, and the active components are difficult to be released, which limits the efficacy of the active components. The other is to make the spinning first, and then attach the active components to the outside of the spinning. The spinning prepared in this way has good active component release performance, but the active components are easy to fall off after washing, and the anti-washing effect is not good.

[0006] In order to develop a viscose biofiber with good antioxidant effect and good washing resistance, we proposed a viscose biofiber containing antioxidant active ingredients and a preparation method thereof. Summary of the invention

[0007] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a viscose large biological fiber containing antioxidant active ingredients and a preparation method thereof.

[0008] A viscose biofiber containing antioxidant active ingredients is prepared by reacting the following raw materials in parts by weight: 20-24 parts of COFs carrier, 5-8 parts of plant-derived antioxidant active components, 200-240 parts of spinning stock solution, 2-4 parts of sodium lauryl sulfate, 2-4 parts of glycerol monooleate, 3-5 parts of cyclodextrin, 2-4 parts of titanium dioxide and 3-5 parts of silane coupling agent.

[0009] Preferably, the preparation method of the plant-derived antioxidant active component comprises the following steps: wetting tea leaves with deionized water, and then freeze-drying them, then washing grapes with deionized water and squeezing them into grape juice, soaking the freeze-dried tea leaves in the grape juice, soaking them at 0-5°C for 10-12h, ultrasonically treating them for 15-30min after soaking, and then filtering them once, evaporating and crystallizing the obtained filtrate once to obtain a solid mixture, crushing the solid mixture into powder, adding the powder into anhydrous ethanol, ultrasonically treating them for 15-30min, and then filtering them twice, collecting the filtrate for secondary evaporation and crystallization to obtain the plant-derived antioxidant active component;

[0010] The mass ratio of tea to grape is 1:15-20.

[0011] Preferably, in the process of preparing the plant-derived antioxidant active component, seeded grapes are selected, and when the grapes are washed with deionized water and squeezed into grape juice, the grape skins, grape pulp and grape seeds are all crushed.

[0012] Preferably, during the preparation of the plant-derived antioxidant active component, the frequency of the ultrasonic treatment is 22-24 kHz and the power is 400-500W.

[0013] Preferably, in the process of preparing the plant-derived antioxidant active components, the tea leaves used are unfermented tea leaves or slightly fermented tea leaves.

[0014] Preferably, in the spinning solution, the α-cellulose content is 8.1%-8.3%, the sodium hydroxide content is 5.5%-6%, and the viscosity is 45-55s.

[0015] Preferably, the particle size of the nano titanium dioxide is 10-20 nm.

[0016] Preferably, a method for preparing viscose large biofiber containing antioxidant active ingredients comprises the following steps:

[0017] Step 1, COFs carrier modification: titanium dioxide and silane coupling agent are fully mixed, and then added to an ethanol solution, and plant-derived antioxidant active components, sodium dodecyl sulfate, glycerol monooleate and cyclodextrin are added under stirring, stirred and heated to 65-75°C, stirred and refluxed for 5-8h, and then ethanol is evaporated to dryness to obtain modified COFs;

[0018] Step 2, preparing a spinning solution: fully mixing the modified COFs and the spinning solution to obtain a spinning solution;

[0019] Step 3, spinning: using a spinning solution for spinning treatment to obtain viscose large biofibers containing antioxidant active ingredients.

[0020] Preferably, in step 3, the spinning solution is poured into a spinning machine and spun at a spinning speed of 15-18 m / min. The spinning is carried out in a coagulation bath at a temperature of 30-35°C. After spinning and solidification, the solution is desulfurized, washed, oiled and dried to obtain viscose large bio-fibers containing antioxidant active ingredients.

[0021] Preferably, in step 3, the contents of the components in the coagulation bath are: 115-120 g / L sulfuric acid, 220-240 g / L sodium sulfate, and 12-15 g / L zinc sulfate.

[0022] The beneficial effects of the present invention are:

[0023] 1. In the preparation process of the viscose large bio-fiber prepared by the present invention, the antioxidant active components are attached to the COFs carrier. In the prepared viscose large bio-fiber, the COFs carrier serves as the skeleton of the viscose large bio-fiber, and the end of the COFs carrier is exposed or close to the epidermis of the viscose large bio-fiber, which facilitates the transfer of the active components on the COFs carrier to the epidermis of the viscose large bio-fiber, ensuring that the active components can play a role smoothly, and the viscose large bio-fiber has a good antioxidant effect.

[0024] 2. The viscose bio-fiber prepared by the present invention has plant-derived antioxidant active components added during the preparation process, which effectively improves the environmental performance of the viscose bio-fiber; in the preparation process of the plant-derived antioxidant active components, the active components in tea and grapes are effectively retained, thereby improving the antioxidant properties of the viscose bio-fiber.

[0025] 3. The viscose biofiber prepared by the present invention is prepared by adding titanium dioxide and a silane coupling agent during the preparation process. The titanium dioxide wrapped by the silane coupling agent has certain photocatalytic properties and can improve the antioxidant properties of the viscose biofiber. DETAILED DESCRIPTION

[0026] The present invention will be further explained below in conjunction with specific embodiments.

[0027] In the following embodiments, the experimental methods or test methods, unless otherwise specified, are conventional methods; reagents and materials, unless otherwise specified, are obtained from conventional commercial channels or prepared by conventional methods, wherein: α-cellulose was purchased from Shanghai Moxian Industrial Co., Ltd.; nano-titanium dioxide was purchased from Jiangsu Caiwei Biotechnology Co., Ltd.; cyclodextrin was purchased from Shandong Tongwang Biotechnology Co., Ltd.; sodium dodecyl sulfate and glycerol monooleate were purchased from Jiangsu Pules Biotechnology Co., Ltd.; silane coupling agent KH560 was purchased from Jiangsu Jiujia Biotechnology Co., Ltd.

[0028] In the following examples, the preparation method of the COFs carrier comprises the following steps:

[0029] 108.6 mg of 2,4,6-tris(4-aminophenyl)1.3,5-triazine and 105 mg of 2,3,5,6-tetrafluoroterephthalaldehyde were mixed in a glass tube, and then 2 mL of 1,2-dichlorobenzene and 4 mL of n-butanol were added. The mixed solution was ultrasonically treated for 20 min and then 1 mL of 6 M acetic acid aqueous solution was added to obtain a uniformly dispersed yellow solution; the yellow solution was treated with nitrogen-freeze-degassing 5 times to remove oxygen in the yellow solution, and then dried in a drying oven at 120°C and heated for 3 days. Finally, the product was centrifuged and washed with tetrahydrofuran, acetone, and methanol, respectively, and then filtered with n-hexane and placed in a vacuum drying oven at 60°C for 12 hours to obtain an orange-yellow solid powder, which is the desired COFs carrier.

[0030] In Example 1, a viscose large biofiber containing antioxidant active ingredients is prepared by reacting the following raw materials in parts by weight: 20 parts of COFs carrier, 5 parts of plant-derived antioxidant active components, 200 parts of spinning stock solution, 2 parts of sodium dodecyl sulfate, 2 parts of glycerol monooleate, 3 parts of cyclodextrin, 2 parts of titanium dioxide and 3 parts of silane coupling agent.

[0031] The preparation method of plant-derived antioxidant active components comprises the following steps: wetting tea leaves with deionized water and then freeze-drying them, washing grapes with deionized water and squeezing them into grape juice, soaking the freeze-dried tea leaves in the grape juice at 0°C for 10 hours, ultrasonically treating them for 15 minutes after the soaking, filtering them once, evaporating and crystallizing the obtained filtrate once to obtain a solid mixture, crushing the solid mixture into powder, adding the powder into anhydrous ethanol, ultrasonically treating them for 15 minutes, and then filtering them twice, collecting the filtrate and performing secondary evaporation and crystallization to obtain plant-derived antioxidant active components;

[0032] The mass ratio of tea to grape is 1:15.

[0033] In the process of preparing the plant-derived antioxidant active component, seeded grapes are selected, and when the grapes are washed with deionized water and squeezed into grape juice, the grape skins, grape pulps and grape seeds are all crushed.

[0034] During the preparation of the plant-derived antioxidant active components, the frequency of ultrasonic treatment was 22 kHz and the power was 400 W.

[0035] In the process of preparing plant-derived antioxidant active components, green tea is selected.

[0036] In the spinning solution, the α-cellulose content is 8.1%, the sodium hydroxide content is 5.5%, and the viscosity is 45s.

[0037] The particle size of nano titanium dioxide is 10-20nm.

[0038] A method for preparing viscose large biofiber containing antioxidant active ingredients comprises the following steps:

[0039] Step 1, COFs carrier modification: titanium dioxide and silane coupling agent are fully mixed, and then added to an ethanol solution, and plant-derived antioxidant active components, sodium dodecyl sulfate, glycerol monooleate and cyclodextrin are added under stirring, stirred and heated to 65°C, stirred and refluxed for 5 hours, and then ethanol is evaporated to dryness to obtain modified COFs;

[0040] Step 2, preparing a spinning solution: fully mixing the modified COFs and the spinning solution to obtain a spinning solution;

[0041] Step 3, spinning: using a spinning solution for spinning treatment to obtain viscose large biofibers containing antioxidant active ingredients.

[0042] In step 3, the spinning solution is poured into a spinning machine and spun at a spinning speed of 15 m / min. The spinning is carried out in a coagulation bath at a temperature of 30°C. After spinning and solidification, the fiber is desulfurized, washed, oiled and dried to obtain viscose large biofibers containing antioxidant active ingredients.

[0043] In step 3, the contents of the components in the coagulation bath are: 115 g / L sulfuric acid, 220 g / L sodium sulfate, and 12 g / L zinc sulfate.

[0044] In Example 2, a viscose large biofiber containing antioxidant active ingredients is prepared by reacting the following raw materials in parts by weight: 24 parts of COFs carrier, 8 parts of plant-derived antioxidant active components, 240 parts of spinning stock solution, 4 parts of sodium dodecyl sulfate, 4 parts of glycerol monooleate, 5 parts of cyclodextrin, 4 parts of titanium dioxide and 5 parts of silane coupling agent.

[0045] The preparation method of plant-derived antioxidant active components comprises the following steps: wetting tea leaves with deionized water and then freeze-drying them, washing grapes with deionized water and squeezing them into grape juice, soaking the freeze-dried tea leaves in the grape juice at 5°C for 12 hours, ultrasonically treating them for 30 minutes after the soaking, filtering them once, evaporating and crystallizing the obtained filtrate once to obtain a solid mixture, crushing the solid mixture into powder, adding the powder into anhydrous ethanol, ultrasonically treating them for 30 minutes, and then filtering them twice, collecting the filtrate and performing secondary evaporation and crystallization to obtain plant-derived antioxidant active components;

[0046] The mass ratio of tea to grape is 1:20.

[0047] In the process of preparing the plant-derived antioxidant active component, seeded grapes are selected, and when the grapes are washed with deionized water and squeezed into grape juice, the grape skins, grape pulps and grape seeds are all crushed.

[0048] During the preparation of the plant-derived antioxidant active components, the frequency of ultrasonic treatment was 24 kHz and the power was 500 W.

[0049] In the process of preparing plant-derived antioxidant active components, white tea is selected.

[0050] In the spinning solution, the α-cellulose content is 8.3%, the sodium hydroxide content is 6%, and the viscosity is 55s.

[0051] The particle size of nano titanium dioxide is 10-20nm.

[0052] A method for preparing viscose large biofiber containing antioxidant active ingredients comprises the following steps:

[0053] Step 1, COFs carrier modification: titanium dioxide and silane coupling agent are fully mixed, and then added to an ethanol solution, and plant-derived antioxidant active components, sodium dodecyl sulfate, glycerol monooleate and cyclodextrin are added under stirring, stirred and heated to 75°C, stirred and refluxed for 8 hours, and then ethanol is evaporated to dryness to obtain modified COFs;

[0054] Step 2, preparing a spinning solution: fully mixing the modified COFs and the spinning solution to obtain a spinning solution;

[0055] Step 3, spinning: using a spinning solution for spinning treatment to obtain viscose large biofibers containing antioxidant active ingredients.

[0056] In step 3, the spinning solution is poured into a spinning machine and spun at a spinning speed of 18 m / min. The spinning is carried out in a coagulation bath at a temperature of 35°C. After spinning and solidification, the fiber is desulfurized, washed, oiled and dried to obtain viscose large biofibers containing antioxidant active ingredients.

[0057] In step 3, the contents of the components in the coagulation bath are: 120 g / L sulfuric acid, 240 g / L sodium sulfate, and 15 g / L zinc sulfate.

[0058] In Example 3, a viscose large biofiber containing antioxidant active ingredients is prepared by reacting the following raw materials in parts by weight: 22 parts of COFs carrier, 6 parts of plant-derived antioxidant active components, 220 parts of spinning stock solution, 3 parts of sodium dodecyl sulfate, 3 parts of glycerol monooleate, 4 parts of cyclodextrin, 3 parts of titanium dioxide and 4 parts of silane coupling agent.

[0059] The preparation method of plant-derived antioxidant active components comprises the following steps: wetting tea leaves with deionized water and then freeze-drying them, washing grapes with deionized water and squeezing them into grape juice, soaking the freeze-dried tea leaves in the grape juice at 3°C ​​for 11 hours, ultrasonically treating them for 18 minutes after the soaking, filtering them once, evaporating and crystallizing the obtained filtrate once to obtain a solid mixture, crushing the solid mixture into powder, adding the powder into anhydrous ethanol, ultrasonically treating them for 18 minutes, and then filtering them twice, collecting the filtrate and performing secondary evaporation and crystallization to obtain plant-derived antioxidant active components;

[0060] The mass ratio of tea to grape is 1:16.

[0061] In the process of preparing the plant-derived antioxidant active component, seeded grapes are selected, and when the grapes are washed with deionized water and squeezed into grape juice, the grape skins, grape pulps and grape seeds are all crushed.

[0062] During the preparation of the plant-derived antioxidant active components, the frequency of ultrasonic treatment was 23 kHz and the power was 450 W.

[0063] In the process of preparing plant-derived antioxidant active components, green tea is selected.

[0064] In the spinning solution, the α-cellulose content is 8.2%, the sodium hydroxide content is 5.7%, and the viscosity is 50s.

[0065] The particle size of nano titanium dioxide is 10-20nm.

[0066] A method for preparing viscose large biofiber containing antioxidant active ingredients comprises the following steps:

[0067] Step 1, COFs carrier modification: titanium dioxide and silane coupling agent are fully mixed, and then added to an ethanol solution, and plant-derived antioxidant active components, sodium dodecyl sulfate, glycerol monooleate and cyclodextrin are added under stirring, stirred and heated to 70°C, stirred and refluxed for 6 hours, and then ethanol is evaporated to dryness to obtain modified COFs;

[0068] Step 2, preparing a spinning solution: fully mixing the modified COFs and the spinning solution to obtain a spinning solution;

[0069] Step 3, spinning: using a spinning solution for spinning treatment to obtain viscose large biofibers containing antioxidant active ingredients.

[0070] In step 3, the spinning solution is poured into a spinning machine and spun at a spinning speed of 16 m / min. The spinning is carried out in a coagulation bath at a temperature of 32° C. After spinning and solidification, the fiber is desulfurized, washed, oiled, and dried to obtain viscose large biofibers containing antioxidant active ingredients.

[0071] In step 3, the contents of the components in the coagulation bath are: 118 g / L sulfuric acid, 230 g / L sodium sulfate, and 13 g / L zinc sulfate.

[0072] In Comparative Example 1, compared with Example 3, the raw material for preparing the viscose large biofiber for antioxidant active ingredients does not contain plant-derived antioxidant active components, and the other parts are the same as Example 3.

[0073] In Comparative Example 2, compared with Example 3, the raw material for preparing the viscose large biofiber for antioxidant active ingredients does not contain the COFs carrier, and the other parts are the same as Example 3.

[0074] In Comparative Example 3, compared with Example 3, the raw material for preparing the viscose large biofiber with antioxidant active ingredients does not contain titanium oxide and silane coupling agent, and the other parts are the same as Example 3.

[0075] In Comparative Example 4, compared with Example 3, the preparation method of the plant-derived antioxidant active component is different, and the preparation method of the plant-derived antioxidant active component comprises the following steps: wetting the tea leaves with deionized water, and then freeze-drying the tea leaves, soaking the freeze-dried tea leaves in deionized water, and soaking them at 3°C ​​for 11 hours, then washing the grapes with deionized water and squeezing them into grape juice, mixing the grape juice with the tea soaking liquid, ultrasonically treating them for 18 minutes after the mixing is completed, and then filtering them once, evaporating and crystallizing the obtained filtrate once to obtain a solid mixture, crushing the solid mixture into powder, adding the powder into anhydrous ethanol, ultrasonically treating it for 18 minutes, and then filtering them twice, collecting the filtrate for secondary evaporation and crystallization to obtain the plant-derived antioxidant active component;

[0076] The mass ratio of tea leaves to grapes is 1:16. Other parts are the same as those in Example 3.

[0077] The following performance tests were performed on Examples 1-3 and Comparative Examples 1-4: The test contents included DPPH free radical scavenging test and ABTS + Free radical scavenging experiment.

[0078] 1. DPPH free radical scavenging experiment: prepare 100×10 -6 M DPPH solution, take 10 ml of the solution as 1 portion, add 1 g of the viscose large biofiber prepared in Examples 1-3 and Comparative Examples 1-4 to each portion, record its ultraviolet absorption at 519 nm, detect the absorbance of the mixture after reacting for 30 minutes under dark conditions, and calculate the DPPH free radical scavenging rate.

[0079] 2. ABTS + · Free radical scavenging experiment: prepare 100×10 -6 ABTS of M + The solute is ABTS diammonium salt, 10 ml of the solution is taken as 1 portion, 1 g of the viscose large biofiber prepared in Examples 1-3 and Comparative Examples 1-4 is added to each portion, and its ultraviolet absorption at 734 nm is recorded. After reacting for 30 minutes in the dark, the absorbance of the mixture is detected to calculate the ABTS free radical scavenging rate.

[0080] The measurement results are shown in Table 1.

[0081] Table 1

[0082]

[0083] From Table 1, it can be seen that the viscose large biofiber prepared in Examples 1-3 has excellent antioxidant properties and a high free radical scavenging rate, and after multiple washings, the free radical scavenging rate has a small change range and is relatively stable. In Comparative Example 1, no plant-derived antioxidant active components are included, and its free radical scavenging rate decreases significantly; in Comparative Example 2, no COFs carrier is included, resulting in inconvenient transfer of active components, and its free radical scavenging rate decreases significantly, which is slightly better than Comparative Example 1. After multiple washings, the free radical scavenging rate remains almost unchanged; in Comparative Example 3, titanium oxide and silane coupling agent are not added, and its free radical scavenging rate decreases slightly; in Comparative Example 4, the preparation method of its plant-derived antioxidant active components is different, resulting in a significant decrease in its free radical scavenging rate.

[0084] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A viscose biofiber containing antioxidant active ingredients, characterized in that: The invention is prepared by reacting the following raw materials in parts by weight: 20-24 parts of COFs carrier, 5-8 parts of plant-derived antioxidant active components, 200-240 parts of spinning solution, 2-4 parts of sodium lauryl sulfate, 2-4 parts of glycerol monooleate, 3-5 parts of cyclodextrin, 2-4 parts of titanium dioxide and 3-5 parts of silane coupling agent.

2. The viscose biofiber containing antioxidant active ingredients according to claim 1, characterized in that: The preparation method of the plant-derived antioxidant active component comprises the following steps: wetting tea leaves with deionized water and then freeze-drying them, washing grapes with deionized water and squeezing them into grape juice, soaking the freeze-dried tea leaves in the grape juice at 0-5°C for 10-12 hours, ultrasonically treating them for 15-30 minutes after the soaking, filtering them once, evaporating and crystallizing the obtained filtrate once to obtain a solid mixture, crushing the solid mixture into powder, adding the powder into anhydrous ethanol, ultrasonically treating them for 15-30 minutes, and then filtering them twice, collecting the filtrate and performing secondary evaporation and crystallization to obtain the plant-derived antioxidant active component; The mass ratio of tea to grape is 1:15-20.

3. The viscose biofiber containing antioxidant active ingredients according to claim 2, characterized in that: In the process of preparing the plant-derived antioxidant active component, seeded grapes are selected, and when the grapes are washed with deionized water and squeezed into grape juice, the grape skins, grape pulps and grape seeds are all crushed.

4. The viscose biofiber containing antioxidant active ingredients according to claim 2, characterized in that: In the process of preparing the plant-derived antioxidant active components, the frequency of ultrasonic treatment is 22-24kHz and the power is 400-500W.

5. The viscose biofiber containing antioxidant active ingredients according to claim 2, characterized in that: In the process of preparing plant-derived antioxidant active components, unfermented tea or slightly fermented tea is selected.

6. The viscose biofiber containing antioxidant active ingredients according to claim 1, characterized in that: In the spinning solution, the α-cellulose content is 8.1%-8.3%, the sodium hydroxide content is 5.5%-6%, and the viscosity is 45-55s.

7. The viscose biofiber containing antioxidant active ingredients according to claim 1, characterized in that: The particle size of the nano titanium dioxide is 10-20 nm.

8. A method for preparing viscose large biofiber containing antioxidant active ingredients according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1, COFs carrier modification: titanium dioxide and silane coupling agent are fully mixed, and then added to an ethanol solution, and plant-derived antioxidant active components, sodium dodecyl sulfate, glycerol monooleate and cyclodextrin are added under stirring, stirred and heated to 65-75°C, stirred and refluxed for 5-8h, and then ethanol is evaporated to dryness to obtain modified COFs; Step 2, preparing a spinning solution: fully mixing the modified COFs and the spinning solution to obtain a spinning solution; Step 3, spinning: using a spinning solution for spinning treatment to obtain viscose large biofibers containing antioxidant active ingredients.

9. The method for preparing a viscose large biofiber containing antioxidant active ingredients according to claim 8, characterized in that: In the step 3, the spinning solution is poured into a spinning machine, and the spinning process is carried out at a spinning speed of 15-18 m / min, and the spinning is carried out in a coagulation bath at a temperature of 30-35° C. After spinning and solidification, the spinning solution is desulfurized, washed, oiled, and dried to obtain viscose large bio-fibers containing antioxidant active ingredients.

10. The method for preparing a viscose large biofiber containing antioxidant active ingredients according to claim 8, characterized in that: In step 3, the contents of the components in the coagulation bath are: 115-120 g / L sulfuric acid, 220-240 g / L sodium sulfate, and 12-15 g / L zinc sulfate.

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