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

Abstract

The invention provides viscose large biological fibers containing olive active ingredients and a preparation method thereof.The viscose large biological fibers are prepared from, by weight, 100 parts of polyester chips, 10-12 parts of olive extract microcapsules with molecular nest structures and 5-7 parts of microcrystalline cellulose dispersants.According to the molecular nest structures, MOF-coated SiO2 porous core-shell frames serve as primary coating layers, and alternately depositing sodium alginate-epsilon-polylysine. According to the viscose large biological fiber containing the olive active ingredients and the preparation method of the viscose large biological fiber, the distribution uniformity of the olive active ingredients in the viscose large biological fiber is improved, and the problem that the fiber functionality and quality stability are poor due to uneven distribution is solved; the stability of the active ingredients of the olea europaea in the processing process is improved, and the problems that the active ingredients of the olea europaea are degraded due to the effects of temperature, illumination, oxygen, high-temperature treatment and chemical reagents, the structure is damaged and the original effect is lost are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fiber manufacturing, in particular to a viscose large bio-fiber containing active ingredients of olea europaea and a preparation method thereof. BACKGROUND

[0002] With the continuous improvement of people's pursuit of life quality and health and environmental protection, the research and application of functional fiber materials have become a hot spot in the field of textiles and related fields. Viscose large bio-fiber, as a fiber material with good biocompatibility and biodegradability, has shown broad application prospects in the fields of clothing, medical treatment, health care, etc. At the same time, olea europaea, as a plant rich in various active ingredients, has significant effects in antioxidant, antibacterial, skin care, etc. The introduction of active ingredients of olea europaea into viscose large bio-fiber is expected to develop new fiber materials with functionality and environmental protection, meeting the market demand for high-quality fiber products.

[0003] Viscose large bio-fiber is a fiber prepared from natural cellulose through specific biological or chemical methods. It not only retains the excellent properties of natural fibers, such as good moisture absorption, air permeability and biocompatibility, but also has biodegradability and is environmentally friendly. Compared with traditional viscose fiber, viscose large bio-fiber uses a more environmentally friendly process in the preparation process, reducing the use of chemical reagents and the emission of waste, meeting the requirements of sustainable development.

[0004] Olea europaea is rich in various active ingredients, mainly including olive polyphenols, oleuropein, vitamin E, unsaturated fatty acids, etc. These ingredients have unique chemical structures and biological activities, endowing olea europaea with various health benefits. Olive polyphenols and oleuropein have strong antioxidant effects, can scavenge free radicals in the body, delay cell aging, and prevent the occurrence of chronic diseases such as cardiovascular diseases. Vitamin E is also an important antioxidant, which synergistically acts with olive polyphenols and oleuropein to enhance the antioxidant effect. Unsaturated fatty acids such as oleic acid and linoleic acid have good moisturizing and moisturizing effects on the skin, can improve the elasticity and luster of the skin, and prevent the occurrence of dry skin and wrinkles. In addition, the active ingredients of olea europaea also have certain antibacterial and anti-inflammatory effects, can inhibit the growth and reproduction of bacteria and fungi, and have certain therapeutic effects on skin inflammation and infection.

[0005] At present, in the preparation of viscose big biological fiber containing active ingredients of olea europaea, the commonly used method is to mix the active ingredients of olea europaea with viscose solution and then spin. However, due to the poor compatibility of the active ingredients of olea europaea and the viscose solution, the active ingredients are prone to uneven distribution in the fiber, affecting the functionality and quality stability of the fiber. The content of active ingredients in some areas is too high, which may have adverse effects on the physical properties of the fiber; while the content of active ingredients in some areas is too low, which cannot achieve the expected functional effect. The active ingredients of olea europaea are easily affected by factors such as temperature, light and oxygen during processing and are prone to degradation, resulting in reduced activity. In the preparation process of viscose big biological fiber, high temperature treatment and chemical reagents are needed, which may destroy the structure of the active ingredients of olea europaea and lose the original efficacy. In addition, the active ingredients may gradually decompose during the storage and use of the fiber, affecting the long-term functionality and service life of the fiber. Based on this, the present application provides a viscose big biological fiber containing active ingredients of olea europaea and a preparation method thereof. SUMMARY

[0006] The purpose of the present application is to provide a viscose big biological fiber containing active ingredients of olea europaea and a preparation method thereof, which improves the uniformity of the distribution of active ingredients of olea europaea in viscose big biological fiber, and improves the problem of poor functionality and quality stability of the fiber caused by uneven distribution; improves the stability of active ingredients of olea europaea during processing, and improves the problem of degradation, structure destruction and loss of original efficacy caused by temperature, light, oxygen, high temperature treatment and chemical reagents.

[0007] In one aspect, the present application provides a viscose big biological fiber containing active ingredients of olea europaea, which comprises the following raw materials by weight: 100 parts of terylene polyester chips, 10-12 parts of olea europaea extract microcapsules with molecular nest structure and 5-7 parts of microcrystalline cellulose dispersant, wherein the molecular nest structure is composed of MOF@SiO2 porous core-shell framework as a primary coating layer and sodium alginate-ε-polylysine alternately deposited.

[0008] Further, the preparation method of the olea europaea extract microcapsules comprises: spraying MOF@SiO2 powder on the surface of the olea europaea extract to obtain a coating material, immersing the coating material in a sodium alginate solution for 3-5 min, washing with water, then immersing it in an ε-polylysine solution for 3-5 min, continuing to wash with water, repeating 3-5 times, and vacuum drying at 45℃ for 5-7h to obtain the olea europaea extract microcapsules.

[0009] Further, the sodium alginate solution is a 0.5%-0.7% sodium alginate aqueous solution with pH=6.5; the ε-polylysine solution is a 0.5%-0.7% ε-polylysine aqueous solution with pH=7.0.

[0010] Further, the MOF@SiO2 powder, the olive extract, the sodium alginate solution and the epsilon-polylysine solution are in a ratio of 20g: 25-35g: 350-450mL: 350-450mL.

[0011] Further, the preparation method of the MOF@SiO2 powder comprises: dispersing Zn-MOF crystals in ethanol, ultrasonicating for 30min to form a uniform suspension, adding cetyltrimethylammonium bromide and stirring at 50-60℃ for 1-2h, adding ammonia water and stirring for 10-15min, then adding tetraethyl orthosilicate and stirring at room temperature for 22-24h, centrifuging, washing and drying to obtain MOF@SiO2.

[0012] Further, the mass concentration of the ammonia water is 28-30%; the Zn-MOF crystals, ethanol, cetyltrimethylammonium bromide, tetraethyl orthosilicate and ammonia water are in a ratio of 1g: 110-130mL: 0.3-0.5g: 0.5-1mL: 1-2mL.

[0013] Further, the preparation method of the Zn-MOF crystals comprises: adding rosmarinic acid and zinc nitrate hexahydrate into a mixed solution of DMF and water, hydrothermal reaction at 110-120℃ for 10-12h, natural cooling to room temperature, centrifuging, washing and drying to obtain Zn-MOF crystals.

[0014] Further, the rosmarinic acid, zinc nitrate hexahydrate, DMF and water are in a ratio of 1-1.5g: 2-2.5g: 40-50mL: 10-15mL.

[0015] In another aspect, the application further provides a preparation method of viscose large biofibers containing olive active ingredients, comprising: mixing polyester chips, olive extract microcapsules and microcrystalline cellulose at a rotation speed of 300-500r / min for 15-20min, adding into a double-screw extruder for extrusion and melting, then spinning to obtain fibers, and then drawing, oiling and winding to obtain the viscose large biofibers containing olive active ingredients.

[0016] Further, the temperature of the first zone of the double-screw extruder is 220-230℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 260-270℃, the temperature of the fourth zone is 270-280℃, and the temperature of the die head is 275-285℃; the rotation speed of the screw is 150-200r / min, and the feeding speed is 10-15kg / h.

[0017] The application has the following beneficial effects:

[0018] (1) In the preparation of the olive extract microcapsule, the MOF@SiO2 powder is deposited on the surface of the olive extract by a spray deposition method to obtain a coating material. The spray deposition can uniformly cover the MOF@SiO2 powder on the surface of the olive extract, form a preliminary protective layer, and reduce the direct contact of the olive extract with the external environment. The formed molecular nest structure is stable, can further isolate the influence of external factors on the olive extract, and has certain mechanical strength and chemical stability, so that the active ingredients of the olive can be protected from being destroyed in the processing process

[0019] (2) In the present application, the Zn-MOF crystal takes rosmarinic acid as the coordination core, and constructs an antibacterial active site through a hydrothermal reaction. The phenolic hydroxyl group in the rosmarinic acid molecule forms a coordination bond with zinc ions, which not only stabilizes the MOF framework structure, but also endows it with broad-spectrum antibacterial activity. The MOF@SiO2 core-shell structure grows a silica layer on the surface of the Zn-MOF through a sol-gel method, and the mesoporous structure can not only act as a slow-release channel for active ingredients, but also shield the thermal degradation effect in the high-temperature processing process. Experiments show that simple SiO2 coating can cause a significant decrease in antibacterial activity, while the core-shell synergistic effect of MOF@SiO2 can maintain the structural integrity of the active ingredients at the processing temperature, while achieving controlled release.

[0020] (3) In the present application, sodium alginate and epsilon-polylysine form a polyelectrolyte composite film through electrostatic interaction, and the alternating deposition process simulates the phospholipid bilayer structure of the cell membrane. The carboxylate of sodium alginate and the amino group of epsilon-polylysine undergo directional self-assembly under the driving of pH gradient, forming a dense cross-linked network. This coating layer with alternating deposition of four times of positive and negative ions has a dual function: the outer layer of epsilon-polylysine endows the fiber surface with positive charge, enhancing the adsorption capacity of negatively charged bacteria; the inner layer of sodium alginate acts as a barrier layer, effectively blocking the penetration of oxygen and water. When the number of deposition times is reduced, the porosity of the coating layer increases, leading to leakage of active ingredients and attenuation of antibacterial efficiency.

[0021] (4) In the present application, the microcrystalline cellulose dispersant realizes the uniform dispersion of the olive extract microcapsule through the space steric effect, and the surface hydroxyl group forms a hydrogen bond network with the amino group on the surface of the microcapsule, constructing a dynamic lubricating layer in the melt spinning process. This dispersion system solves the problem of agglomeration of traditional microcapsules in high-temperature melt, and makes the active ingredients present a gradient distribution in the fiber cross-section: the high-concentration area on the surface layer realizes rapid antibacterial, and the slow-release area in the core layer maintains long-term function. The absence of the dispersant will cause the breaking strength of the fiber to decrease significantly, which confirms the decisive role of micro-nano uniformity on the mechanical properties.

[0022] (5) The technical system in the application builds a complete protection chain from the molecular scale to the macro scale through the triple protection mechanism of MOF@SiO2 core-shell structure, polyelectrolyte multilayer coating and microcrystalline cellulose dispersion. The MOF framework provides antibacterial active elements, the SiO2 shell layer shields thermal degradation, the polyelectrolyte layer blocks environmental erosion, and the dispersion system ensures processing stability. The four form a dynamic balance: when the external environment changes, the polyelectrolyte layer undergoes reversible swelling to adjust the release rate of the active ingredient; the SiO2 shell layer controls the release channel through ion diffusion; the dispersion system ensures the uniform distribution of the microcapsules in the fiber matrix; and this multi-level synergistic effect enables the fiber to maintain more than 90% of the initial antibacterial rate in the washing test, which is much better than the material system with a single protection mechanism. DETAILED DESCRIPTION

[0023] The technical solutions of the application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0024] In the following examples, the raw materials not mentioned are commercially available. The olive extract is purchased from Changsha Shanghe Biological Technology Co., Ltd.; the microcrystalline cellulose, CAS No. 9004-34-6, is purchased from Hebei Zhongzisheng Biological Technology Co., Ltd.; the Staphylococcus aureus is purchased from Shanghai Lumi Technology Co., Ltd., and the Escherichia coli is purchased from Shanghai Lumi Technology Co., Ltd.

[0025] Example 1

[0026] The present embodiment provides a viscose large biological fiber containing olive active ingredients, which comprises the following raw materials by weight: 100 parts of polyester chip, 11 parts of olive extract microcapsules with molecular nest structure and 6 parts of microcrystalline cellulose dispersant; wherein the molecular nest structure is composed of a MOF@SiO2 porous core-shell framework as a primary coating layer and an alternating deposition of sodium alginate and ε-polylysine.

[0027] The preparation method of the viscose large biological fiber containing olive active ingredients comprises the following steps:

[0028] 1.2 g of rosmarinic acid and 2.25 g of zinc nitrate hexahydrate are added to a mixed solution of 45 mL of DMF and 12 mL of water, and the mixture is subjected to hydrothermal reaction at 115℃ for 11 h, naturally cooled to room temperature, centrifuged at 8000 rpm for 10 min, washed with DMF and ethanol for 3 times in sequence, and vacuum dried at 60℃ for 6 h to obtain Zn-MOF crystals.

[0029] MOF@SiO2 was prepared by the following method: 1 g of Zn-MOF crystals was dispersed in 120 mL of ethanol and ultrasonicated for 30 min to form a uniform suspension. Then, 0.4 g of cetyltrimethylammonium bromide was added and stirred at 55 ℃ for 1.5 h. Next, 0.8 mL of ammonia water with a mass concentration of 29% was added and stirred for 12 min. Subsequently, 1.5 mL of tetraethyl orthosilicate was added and stirred at room temperature for 23 h. Finally, the product was centrifuged at 10,000 rpm for 10 min, washed with an ethanol / water (1:1 by volume) mixture for 3 times, and dried at 60 ℃ under vacuum for 12 h.

[0030] The following materials were added to a mixer: 20 g of MOF@SiO2 powder, 0.5 g of magnesium stearate, and 0.1 g of sodium dodecylbenzenesulfonate. The mixture was dry-mixed at 2,000 rpm for 10 min to obtain a mixed material. Then, 30 g of olive extract was loaded into a fluidized bed. The inlet air temperature was 40 ℃, the air flow rate was 0.8 m 3 / min, the bed pressure difference was 200 Pa, and 30 mL of hydroxypropyl methyl cellulose solution with a mass concentration of 1% was sprayed as a spray injection. Subsequently, the mixed material was sprayed and deposited on the surface of the olive extract to obtain a coated material. The powder supply rate was 2 g / min, and the atomization gas pressure was 0.4 MPa. The coated material was immersed in 400 mL of a sodium alginate aqueous solution with pH = 6.5 and a mass concentration of 0.6% for 4 min, washed with water, and then immersed in 400 mL of an ε-polylysine aqueous solution with pH = 7.0 and a mass concentration of 0.6% for 4 min. The water washing was continued, and the above steps were repeated 4 times. Finally, the product was dried at 45 ℃ under vacuum for 6 h to obtain olive extract microcapsules.

[0031] The following materials were mixed at a rotation speed of 400 r / min for 18 min: polyester chip, olive extract microcapsules, and microcrystalline cellulose. The mixture was extruded and melted in a twin-screw extruder with the following parameters: zone 1 temperature: 225 ℃, zone 2 temperature: 245 ℃, zone 3 temperature: 265 ℃, zone 4 temperature: 275 ℃, and die head temperature: 280 ℃. The screw rotation speed was 180 r / min, and the feeding speed was 12 kg / h. Then, the product was spun into fibers, which were drawn, oiled, and wound to obtain viscose biofibers containing olive active ingredients.

[0032] Example 2

[0033] The present embodiment provides a viscose biofiber containing olive active ingredients, which comprises the following raw materials by weight: 100 parts of polyester chip, 10 parts of olive extract microcapsules with a molecular nest structure, and 5 parts of microcrystalline cellulose dispersant. The molecular nest structure is composed of a MOF@SiO2 porous core-shell framework as a primary coating layer and an alternating deposition of sodium alginate and ε-polylysine.

[0034] The preparation method of the viscose biofiber containing olive active ingredients comprises the following steps:

[0035] Zn-MOF crystals were obtained by adding 1 g of rosmarinic acid and 2 g of zinc nitrate hexahydrate into a mixed solution of 40 mL of DMF and 10 mL of water, and then subjecting the mixture to hydrothermal reaction at 110 ℃ for 10 h, followed by natural cooling to room temperature, centrifugation at 8000 rpm for 10 min, washing with DMF, ethanol, and then vacuum drying at 60 ℃ for 6 h;

[0036] The Zn-MOF crystals were dispersed in 110 mL of ethanol, and then subjected to ultrasonic treatment for 30 min to form a uniform suspension. Then, 0.3 g of cetyltrimethylammonium bromide was added, and the mixture was stirred at 50 ℃ for 1 h. Then, 0.5 mL of ammonia water with a mass concentration of 28% was added, and the mixture was stirred for 10 min. Then, 1 mL of tetraethyl orthosilicate was added, and the mixture was stirred at room temperature for 22 h. Then, the mixture was centrifuged at 10000 rpm for 10 min, washed with a mixture of ethanol and water (1:1 by volume) for 3 times, and then vacuum dried at 60 ℃ for 12 h to obtain MOF@SiO2.

[0037] The MOF@SiO2 powder, 0.5 g of magnesium stearate, and 0.1 g of sodium dodecylbenzenesulfonate were added into a mixer, and then dry-mixed at 2000 rpm for 10 min to obtain a mixture. Then, 25 g of olive extract was loaded into a fluidized bed, and the inlet air temperature was set to 40 ℃. The air flow rate was 0.8 m 3 / min, the bed pressure difference was 200 Pa, and 30 mL of hydroxypropyl methyl cellulose aqueous solution with a mass concentration of 1% was sprayed as a spray injection. Then, the mixture was sprayed and deposited on the surface of the olive extract to obtain a coated material. The powder supply rate was 2 g / min, and the atomization gas pressure was 0.4 MPa. Then, the coated material was immersed in 350 mL of 0.5% sodium alginate aqueous solution with pH of 6.5 for 3 min, washed with water, and then immersed in 350 mL of 0.5% ε-polylysine aqueous solution with pH of 7.0 for 3 min, and then washed with water. The above steps were repeated for 3 times, and then the mixture was vacuum dried at 45 ℃ for 5 h to obtain the olive extract microcapsules.

[0038] The polyester chip, the olive extract microcapsules, and the microcrystalline cellulose were mixed at a rotation speed of 300 r / min for 15 min, and then fed into a twin-screw extruder for extrusion and melting. The temperature of the first zone was 220 ℃, the temperature of the second zone was 240 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 270 ℃, and the temperature of the die head was 275 ℃. The screw rotation speed was 150 r / min, and the feeding speed was 10 kg / h. Then, the mixture was spun to obtain a fiber. After the fiber was drawn, oiled, and wound, the viscose bio-fiber containing the active ingredients of the olive extract was obtained.

[0039] Example 3

[0040] The embodiment provides viscose large biofibers containing olive active ingredients, which are prepared from the following raw materials by weight: 100 parts of polyester chip, 12 parts of olive extract microcapsules with molecular nest structure, and 7 parts of microcrystalline cellulose dispersant; wherein the molecular nest structure is composed of a MOF@SiO2 porous core-shell framework as a primary coating layer and sodium alginate-epsilon-polylysine alternately deposited.

[0041] The preparation method of the viscose large biofibers containing olive active ingredients comprises the following steps:

[0042] 1.5 g of rosmarinic acid and 2.5 g of zinc nitrate hexahydrate are added into a mixed solution of 50 mL of DMF and 15 mL of water, and then subjected to hydrothermal reaction at 120 DEG C for 12 h, and then naturally cooled to room temperature, centrifuged at 8000 rpm for 10 min, and then sequentially washed with DMF, ethanol three times, and then vacuum dried at 60 DEG C for 6 h to obtain Zn-MOF crystals;

[0043] 1 g of Zn-MOF crystals is dispersed in 130 mL of ethanol, and then ultrasonically treated for 30 min to form a uniform suspension, 0.5 g of cetyltrimethylammonium bromide is added, and then stirred at 60 DEG C for 1-2 h, 1 mL of ammonia water with a mass concentration of 30% is added, and then stirred for 15 min, 2 mL of tetraethyl orthosilicate is then added, and then stirred at room temperature for 24 h, centrifuged at 10000 rpm for 10 min, sequentially washed with a mixed solution of ethanol / water (volume ratio 1:1) three times, and then vacuum dried at 60 DEG C for 12 h to obtain MOF@SiO2;

[0044] 20 g of MOF@SiO2 powder, 0.5 g of magnesium stearate and 0.1 g of sodium dodecylbenzenesulfonate are added into a mixer, and then dry-mixed at 2000 rpm for 10 min to obtain a mixture; 35 g of olive extract is loaded into a fluidized bed, the inlet air temperature is 40 DEG C, the air volume is 0.8 m 3 / min, the bed pressure difference is 200 Pa, 30 mL of hydroxypropyl methyl cellulose aqueous solution with a mass concentration of 1% is sprayed as an injection, and then the mixture is sprayed and deposited on the surface of the olive extract to obtain a coating material, the powder supply rate is 2 g / min, and the atomization gas pressure is 0.4 MPa; the coating material is immersed in 450 mL of sodium alginate aqueous solution with pH of 6.5 and a mass fraction of 0.7% for 5 min, washed with water, and then immersed in 450 mL of epsilon-polylysine aqueous solution with pH of 7.0 for 5 min, continuously washed with water, and the above steps are repeated for 5 times, and then vacuum dried at 45 DEG C for 7 h to obtain olive extract microcapsules;

[0045] The terylene polyester chip, olive extract microcapsule and microcrystalline cellulose are mixed at a rotation speed of 500 r / min for 20 min, and then added into a double-screw extruder for extrusion melting, the temperature of the first zone is 230℃, the temperature of the second zone is 250℃, the temperature of the third zone is 270℃, the temperature of the fourth zone is 280℃, and the temperature of the die head is 285℃; the screw rotation speed is 200 r / min, and the feeding speed is 15 kg / h; then spinning is performed, the obtained fiber is drawn, oiled and wound to obtain the viscose large bio-fiber containing olive active ingredients.

[0046] Comparative Example 1

[0047] Based on the adjustment of Example 1, different from Example 1 is that no rosemary acid is added in the preparation process of Zn-MOF crystal.

[0048] Comparative Example 2

[0049] Based on the adjustment of Example 1, different from Example 1 is that no Zn-MOF crystal is used. The olive extract is directly coated with SiO2.

[0050] Comparative Example 3

[0051] Based on the adjustment of Example 1, different from Example 1 is that the number of times of alternating deposition of sodium alginate / ε-polylysine is reduced, and only repeated once.

[0052] Comparative Example 4

[0053] Based on the adjustment of Example 1, different from Example 1 is that the step of immersing in 400 mL of pH=6.5, 0.6% sodium alginate aqueous solution for 4 min is not performed, and the step of immersing in ε-polylysine aqueous solution is repeated four times.

[0054] Comparative Example 5

[0055] Based on the adjustment of Example 1, different from Example 1 is that the step of immersing in 400 mL of pH=7.0, 0.6% ε-polylysine aqueous solution for 4 min is not performed, and the step of immersing in sodium alginate aqueous solution is repeated four times.

[0056] Comparative Example 6

[0057] Based on the adjustment of Example 1, different from Example 1 is that the preparation step of the olive extract microcapsule is: 20 g of Zn-MOF, 0.5 g of magnesium stearate and 0.1 g of sodium dodecyl benzene sulfonate are added into a mixer, and dry mixed at 2000 rpm for 10 min to obtain a mixture; 30 g of olive extract is loaded into a fluidized bed, the inlet air temperature is 40℃, the air volume is 0.8 m 3The mixture was sprayed and deposited on the surface of the olive extract to obtain a coating material at a powder supply rate of 2 g / min and an atomizing gas pressure of 0.4 MPa. The coating material was immersed in 400 mL of a 0.6% sodium alginate aqueous solution with pH = 6.5 for 4 min, washed with water, and then immersed in 400 mL of a 0.6% ε-polylysine aqueous solution with pH = 7.0 for 4 min, and washed with water. The above process was repeated 4 times, and the product was vacuum dried at 45°C for 6 h to obtain the olive extract microcapsules.

[0058] Comparative Example 7

[0059] Adjustments were made on the basis of Example 1, and the difference from Example 1 was that no microcrystalline cellulose dispersant was added to the raw materials.

[0060] Comparative Example 8

[0061] Adjustments were made on the basis of Example 1, and the difference from Example 1 was that no olive extract microcapsules with molecular nest structure were added to the raw materials, which served as a blank control.

[0062] Test Example: The properties of the viscose large biofibers prepared in the foregoing Examples 1-4 and Comparative Examples 1-8 were investigated, and the following tests were performed:

[0063] Mechanical property test: The test method was tested in accordance with GB / T 14344, and the test sample was not less than 30, and the test average value was taken;

[0064] Bacteriostatic property test: According to the method in GB / T20944.3-2008, the inhibition rates of Staphylococcus aureus and Escherichia coli of the viscose large biofibers containing olive active ingredients were tested, and the inhibition rates of Staphylococcus aureus and Escherichia coli after 100 times of washing were tested.

[0065] Environmental stability: After aging at 100°C for 168 h, the dry breaking strength was tested, and the dry breaking strength retention rate and the inhibition rates of Staphylococcus aureus and Escherichia coli were calculated;

[0066] The test results are shown in Table 1 below:

[0067] Table 1

[0068]

[0069] In combination with the foregoing, the viscous gluey macrofibers containing the active ingredients of Olea europaea prepared in embodiments 1-3 have excellent comprehensive performance, and the mechanical properties, initial antibacterial rate, washing resistance, and environmental stability are all superior to those of the comparative examples; among them, the Zn-MOF crystal (rosmaninic acid coordination) provides antibacterial activity; the MOF@SiO2 core-shell structure protects the active ingredients; the sodium alginate / ε-polylysine is alternately deposited 4 times to form a dense coating layer; and the microcrystalline cellulose dispersant improves the processing uniformity.

[0070] In comparative example 1, rosmarinic acid is not used in the synthesis of Zn-MOF, and the antibacterial rate drops sharply, which proves that rosmarinic acid is the core of the antibacterial activity of Zn-MOF; in comparative example 2, SiO2 is directly coated (without MOF), and the antibacterial rate decreases, which proves that the MOF@SiO2 core-shell structure is essential for the slow release of the active ingredients; in comparative example 3, the sodium alginate / polylysine deposition is only 1 time, and the antibacterial rate decreases by 15%, which proves that the insufficient density of the coating layer leads to the leakage of the active ingredients; in comparative example 4, the sodium alginate deposition layer is missing, and both the antibacterial rate and the strength decrease, which proves that the integrity of the alternating deposition of anions and cations is destroyed; in comparative example 5, the polylysine deposition layer is missing, which is similar to comparative example 4, and the electrostatic self-assembly coating needs the cooperation of the double layers; in comparative example 6, MOF@SiO2 is not prepared (Zn-MOF is directly used), and the strength drops sharply (6.2 cN / tex), which proves that MOF is not stable at high temperatures, and the SiO2 protective layer cannot be missed; in comparative example 7, there is no microcrystalline cellulose dispersant, and the strength drops sharply (5.9 cN / tex), which proves that the dispersant prevents the agglomeration of microcapsules and ensures the uniformity of melting; and in comparative example 8, there is no blank control, and no Olea europaea extract, which proves that the active ingredients are the source of antibacterial function (antibacterial rate = 0%).

[0071] Finally, it should be noted that the above examples are only used to illustrate the present application and do not limit the technical solutions described in the present application; those skilled in the art should understand that the present application can still be modified or replaced equivalently; and all technical solutions and improvements that do not deviate from the spirit and scope of the present application should be covered in the scope of the claims of the present application.

Claims

1. A viscose biofiber containing olive active ingredients, characterized in that: The invention comprises the following raw materials by weight: 100 parts of polyester chips, 10-12 parts of olive extract microcapsules with a molecular nest structure, and 5-7 parts of microcrystalline cellulose dispersant, wherein the molecular nest structure is composed of a MOF@SiO2 porous core-shell framework as a primary coating layer and alternating deposition of sodium alginate-ε-polylysine.

2. The viscose biofiber containing olive active ingredients according to claim 1, characterized in that: The preparation method of the olive extract microcapsules includes: spraying and depositing MOF@SiO2 powder on the surface of the olive extract to obtain a coating material, immersing the coating material in a sodium alginate solution for 3-5 minutes, washing with water, then immersing it in an ε-polylysine solution for 3-5 minutes, continuing to wash with water, repeating this 3-5 times, and vacuum drying at 45°C for 5-7 hours to obtain the olive extract microcapsules.

3. The viscose biofiber containing olive active ingredients according to claim 2, characterized in that: The sodium alginate solution has a pH of 6.5 and a 0.5%-0.7% sodium alginate aqueous solution; the epsilon-polylysine solution has a pH of 7.0 and a 0.5%-0.7% epsilon-polylysine aqueous solution.

4. The viscose biofiber containing olive active ingredients according to claim 2, characterized in that: The usage ratio of the MOF@SiO2 powder, olive extract, sodium alginate solution and ε-polylysine solution is 20g:25-35g:350-450mL:350-450mL.

5. The viscose biofiber containing olive active ingredients according to claim 2, characterized in that: The preparation method of the MOF@SiO2 powder includes: dispersing Zn-MOF crystals in ethanol, ultrasonicating for 30 minutes to form a uniform suspension, adding hexadecyltrimethylammonium bromide at 50-60°C and stirring for 1-2 hours, adding ammonia water and stirring for 10-15 minutes, then adding ethyl orthosilicate and stirring at room temperature for 22-24 hours, centrifuging, washing, and drying to obtain MOF@SiO2.

6. The viscose biofiber containing olive active ingredients according to claim 5, characterized in that: The mass concentration of the ammonia water is 28-30%; the usage ratio of Zn-MOF crystal, ethanol, hexadecyltrimethylammonium bromide, ethyl orthosilicate and ammonia water is 1g:110-130mL:0.3-0.5g:0.5-1mL:1-2mL.

7. The viscose biofiber containing olive active ingredients according to claim 5, characterized in that: The preparation method of the Zn-MOF crystal comprises: adding rosmarinic acid and zinc nitrate hexahydrate to a mixed solution of DMF and water, performing a hydrothermal reaction at 110-120° C. for 10-12 hours, naturally cooling to room temperature, centrifuging, washing, and drying to obtain the Zn-MOF crystal.

8. The viscose biofiber containing olive active ingredients according to claim 7, characterized in that: The usage ratio of rosmarinic acid, zinc nitrate hexahydrate, DMF and water is 1-1.5 g: 2-2.5 g: 40-50 mL: 10-15 mL.

9. A method for preparing a viscose biofiber containing olive active ingredients according to any one of claims 1 to 8, characterized in that the steps include: Polyester chips, olive extract microcapsules and microcrystalline cellulose are mixed at a rotation speed of 300-500 r / min for 15-20 minutes, added into a twin-screw extruder for extrusion and melting, and then spun to obtain fibers. The fibers are then drawn, oiled and wound to obtain viscose biofibers containing olive active ingredients.

10. The method for preparing the viscose biofiber containing olive active ingredients according to claim 9, characterized in that: The temperature of the first zone of the twin-screw extruder is 220-230°C, the temperature of the second zone is 240-250°C, the temperature of the third zone is 260-270°C, the temperature of the fourth zone is 270-280°C, and the head temperature is 275-285°C; the screw speed is 150-200r / min, and the feeding rate is 10-15kg / h.

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