CN111621873A - Hyaluronic acid fiber and preparation method and application thereof - Google Patents

Hyaluronic acid fiber and preparation method and application thereof Download PDF

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Publication number
CN111621873A
CN111621873A CN202010653233.7A CN202010653233A CN111621873A CN 111621873 A CN111621873 A CN 111621873A CN 202010653233 A CN202010653233 A CN 202010653233A CN 111621873 A CN111621873 A CN 111621873A
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China
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hyaluronic acid
sodium hyaluronate
fiber
ion exchange
exchange resin
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刘翔鸥
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Shenzhen Qianwei Ecological Textile Co ltd
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Shenzhen Qianwei Ecological Textile Co ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to a fiber and a preparation method technology thereof, in particular to a hyaluronic acid fiber and a preparation method and application thereof. The invention provides a hyaluronic acid fiber, which comprises, by weight, 4-12 parts of hyaluronic acid slurry and 88-96 parts of spinning stock solution. The hyaluronic acid serous fluid comprises sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of (0.8-2): (94.6-97.8): (0.8-3.4). The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35. and stirring and mixing the hyaluronic acid slurry and the spinning stock solution for 40-60 minutes to obtain a mixed spinning solution, and then preparing the hyaluronic acid fiber according to a wet spinning process. The fiber prepared by the invention contains hyaluronic acid, and the hyaluronic acid is easy to basically not fall off after being washed for many times.

Description

Hyaluronic acid fiber and preparation method and application thereof
Technical Field
The invention relates to a fiber and a preparation method technology thereof, in particular to a hyaluronic acid fiber and a preparation method and application thereof.
Background
In recent years, with the change of life style and the improvement of living standard of people, the textile industry is changing according to the needs of people. Comfortable heat preservation, health care, antibiosis, beauty and face nourishing become new requirements of people for textiles.
Hyaluronic acid is also called hyaluronic acid, the basic structure of hyaluronic acid is a large polysaccharide consisting of two disaccharide units, namely D-glucuronic acid and N-acetylglucosamine, commercial hyaluronic acid generally refers to sodium salt thereof, namely sodium hyaluronate, but is still called hyaluronic acid in a habitual way, and an aqueous solution of sodium hyaluronate has excellent moisture retention, viscoelasticity and lubricity, is an ideal moisture retention factor, can play a unique role in protecting skin when being used in cosmetics, and is also applied to fabric through related research reports, so that when people wear clothes made of the fabric, the hyaluronic acid has a beneficial effect on human skin. At present, the research on the application of hyaluronic acid to the fabric mainly comprises two methods: (1) soaking the fiber in a solution prepared from hyaluronic acid, draining to obtain modified fiber, and making fabric by using the modified fiber; (2) and soaking the fabric in hyaluronic acid finishing liquid, and then fixing hyaluronic acid on the fabric through crosslinking and curing.
The fiber is mainly used for providing the warm-keeping and moisture-keeping fiber aiming at the northern cold and dry climate environment, and the fabric prepared from the fiber belongs to warm down fabrics, and has the warm-keeping performance and excellent antibacterial and moisture-keeping performance. Although the fabric with the moisturizing performance prepared by using the hyaluronic acid is available, the moisturizing effect is not long enough, or the hyaluronic acid is easy to fall off after the fabric is washed for many times.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a hyaluronic acid fiber, the raw materials of which include hyaluronic acid slurry and spinning dope.
As a preferred technical scheme of the invention, the raw materials of the hyaluronic acid fiber comprise, by weight, 4-12 parts of hyaluronic acid slurry and 88-96 parts of spinning stock solution.
As a preferred technical scheme of the invention, the hyaluronic acid serous fluid comprises the following raw materials in percentage by weight (0.8-2): (94.6-97.8): (0.8-3.4).
According to a preferable technical scheme of the invention, the raw materials of the spinning solution comprise wool fibers, cotton fibers and ionic liquid, wherein the weight ratio of the wool fibers to the cotton fibers to the ionic liquid is 50: 15: 35;
the ionic liquid is selected from one or two of 1-butyl-4-methylmorpholine bromide, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylpyridine iodide, 1-butyl-3-methylpyridine bromide, 1, 3-dibutylbenzimidazole bromide and 1, 3-dibutylbenzotriazole bromide;
the preparation process of the spinning solution comprises the following steps: adding wool fibers, cotton fibers and ionic liquid into a high-pressure digestion tank, introducing inert gas for 25-40 minutes, reacting for 8-12 hours at 80-120 ℃, and then cooling to room temperature to obtain spinning stock solution;
the inert gas is selected from helium, neon and argon.
In a preferred embodiment of the present invention, the ionic liquid is 1-butyl-3-methylpyridine bromide.
The second aspect of the invention provides a preparation method of the hyaluronic acid fiber, and the preparation process of the hyaluronic acid fiber comprises the following steps: and stirring and mixing the hyaluronic acid slurry and the spinning stock solution for 40-60 minutes to obtain a mixed spinning solution, and then preparing the hyaluronic acid fiber according to a wet spinning process.
As a preferred technical scheme of the invention, the hyaluronic acid slurry is prepared by the following processes:
dissolving sodium hyaluronate in deionized water, stirring at room temperature until the sodium hyaluronate is completely dissolved to obtain a sodium hyaluronate aqueous solution, adding an auxiliary agent into the sodium hyaluronate aqueous solution, and stirring at 50-75 ℃ for 2-5 hours to obtain hyaluronic acid slurry.
As a preferable technical scheme of the invention, the auxiliary agent comprises the following raw materials: AgNO3Aqueous solutions, ion exchange resins;
the ion exchange resin is selected from one of Amberlite IRN160 ion exchange resin, Amberlyst 15 ion exchange resin, Amberlite200CNa ion exchange resin and AMBERLITE IR120 Na ion exchange resin;
the preparation process of the auxiliary agent comprises the following steps: adding 50g of ion exchange resin into a container, adding 250m L-0.25 mol/L silver nitrate aqueous solution into the ion exchange resin, uniformly mixing, performing ultrasonic treatment at room temperature for 20 minutes, standing for 12 hours, washing and filtering with deionized water and methanol respectively, and finally drying in a vacuum drying oven at 100 ℃ to constant weight to obtain the auxiliary agent.
As a preferred technical scheme of the invention, the ion exchange resin is Amberlyst 15 ion exchange resin.
The third aspect of the invention provides that the hyaluronic acid fiber can be applied to textile fabrics.
Has the advantages that:
1. the prepared fiber and fabric contain hyaluronic acid, so that when people wear clothes made of the fabric, the fiber and fabric can moisten and moisturize the skin of people and dry cutin, so that the skin is lasting and fine, and the function of skin barrier is enhanced;
amberlyst 15 is a large-mesh structure, has large aperture and excellent adsorption performance, and the hyaluronic acid slurry is better combined with spinning stock solution due to extremely strong adsorption capacity, so that the moisture retention effect of the prepared fabric is more durable, and the hyaluronic acid basically does not fall off after being washed for many times;
3. the introduced Ag ensures that the hyaluronic acid fiber has excellent bacteriostatic property;
4. the wool fibers and the cotton fibers have excellent warm-keeping effect, so that the prepared fabric has warm-keeping performance;
the introduction of Amberlyst 15 increases the mechanical properties of the fiber.
Detailed Description
The invention provides a hyaluronic acid fiber, which comprises hyaluronic acid slurry and spinning solution.
The raw materials of the hyaluronic acid fiber comprise, by weight, 4-12 parts of hyaluronic acid slurry and 88-96 parts of spinning stock solution.
The hyaluronic acid serous fluid comprises sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of (0.8-2): (94.6-97.8): (0.8-3.4).
The sodium hyaluronate comprises one or more of macromolecular hyaluronic acid (with a molecular weight range of 1800000-2200000D), medium molecular hyaluronic acid (with a molecular weight range of 1000000-1800000D) and small molecular hyaluronic acid (with a molecular weight range of 400000-1000000D).
Preferably, the mixture of the macromolecular sodium hyaluronate, the medium molecular sodium hyaluronate and the small molecular sodium hyaluronate is selected.
More preferably, the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate to the small molecular sodium hyaluronate is 12: 35: 53.
the macromolecular sodium hyaluronate, the medium molecular sodium hyaluronate and the small molecular sodium hyaluronate are all purchased from Xian Tongze biotechnology limited company.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is selected from one or two of 1-butyl-4-methylmorpholine bromide, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylpyridine iodide, 1-butyl-3-methylpyridine bromide, 1, 3-dibutylbenzimidazole bromide and 1, 3-dibutylbenzotriazole bromide.
The preparation process of the spinning solution comprises the following steps: adding the wool fibers, the cotton fibers and the ionic liquid into a high-pressure digestion tank, introducing inert gas for 25-40 minutes, reacting for 8-12 hours at 80-120 ℃, and then cooling to room temperature to obtain the spinning solution.
The inert gas is selected from helium, neon and argon.
Preferably, the ionic liquid is 1-butyl-3-methylpyridine bromide salt.
The preparation method of the 1-butyl-3-methylpyridine bromide salt comprises the following steps: 23.7g of pyridine and 55.2g of n-butyl iodide are respectively taken to be put into a flask to react for 4 hours at the temperature of 100 ℃, then the mixture is washed by ether and filtered, and finally the mixture is dried in vacuum at the temperature of 75 ℃ until the weight is constant to prepare the 1-butyl-3-methylpyridine bromide salt.
The second aspect of the invention provides a preparation method of the hyaluronic acid fiber, and the preparation process of the hyaluronic acid fiber comprises the following steps: and stirring and mixing the hyaluronic acid slurry and the spinning stock solution for 40-60 minutes to obtain a mixed spinning solution, and then preparing the hyaluronic acid fiber according to a wet spinning process.
The wet spinning process is a conventional preparation process and comprises the following specific steps: adding the mixed spinning solution into an injector of a wet spinning machine, controlling the spinning speed to be 1.5mL/h by using a flow pump, spinning the spinning solution into distilled water at 60 ℃ under the conditions of 0.2MPa pressure and 115 ℃, naturally solidifying for 30s, and finally washing, oiling and drying to obtain the hyaluronic acid fiber.
The hyaluronic acid slurry is prepared by the following process:
dissolving sodium hyaluronate in deionized water, stirring at room temperature until the sodium hyaluronate is completely dissolved to obtain a sodium hyaluronate aqueous solution, adding an auxiliary agent into the sodium hyaluronate aqueous solution, and stirring at 50-75 ℃ for 2-5 hours to obtain hyaluronic acid slurry.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, ion exchange resin.
The ion exchange resin is selected from one of Amberlite IRN160 ion exchange resin, Amberlyst 15 ion exchange resin, Amberlite200CNa ion exchange resin and AMBERLITE IR120 Na ion exchange resin;
the preparation process of the auxiliary agent comprises the following steps: adding 50g of ion exchange resin into a container, adding 250m L-0.25 mol/L silver nitrate aqueous solution into the ion exchange resin, uniformly mixing, performing ultrasonic treatment at room temperature for 20 minutes, standing for 12 hours, washing and filtering with deionized water and methanol respectively, and finally drying in a vacuum drying oven at 100 ℃ to constant weight to obtain the auxiliary agent.
Preferably, the ion exchange resin is ground to an average particle size of 60 to 85 μm by an ultrafine powder processing device before use.
More preferably, the ion exchange resin is Amberlyst 15 ion exchange resin.
The ion exchange resins are all from the Rohm-Haas company.
The third aspect of the invention provides that the hyaluronic acid fiber can be applied to textile fabrics.
The hyaluronic acid fiber can be prepared into the fabric which has the functions of moistening and drying cutin, enabling skin to be lasting and fine, strengthening skin barrier and having excellent heat preservation performance according to the conventional fabric preparation process.
The conventional fabric preparation process comprises the following steps: the fabric can be obtained by spinning, warping, sizing, denting, weaving, printing and dyeing, drying, shaping, carding, shearing and final shaping.
The larger the molecular weight of the sodium hyaluronate is, the stronger the water absorption and storage capacity is, but the poorer the permeability is; on the contrary, sodium hyaluronate has smaller molecular mass and strong permeability, can enter a dermis layer to improve the water storage capacity of the dermis layer, but has poor film forming capacity and can not lock the moisture on the surface layer of the skin. The applicant has unexpectedly found that: the dry breaking strength of the fibers can be increased by adding the auxiliary agent, the moisturizing effect of the prepared fabric is more durable, the hyaluronic acid is easy to not fall off basically after being washed for many times, and preferably, the hyaluronic acid slurry comprises sodium hyaluronate, deionized water and the auxiliary agent in a weight ratio of 1.2: 96.3: 2.5, by analysis, the possible causes are: the main raw material in the auxiliary agent is Amberlyst 15 ion exchange resin, and the Amberlyst 15 ion exchange resin has a good pore structure and a large specific surface area, so that sodium hyaluronate can be better adsorbed on the surface and in pore channels and is not easy to fall off; the prepared hyaluronic acid slurry contains Amberlyst 15 ion exchange resin, the spinning solution contains 1-butyl-3-methylpyridine iodide, the Amberlyst 15 ion exchange resin is acidic, an acidic site can be used as a substituent, a molecular framework in the 1-butyl-3-methylpyridine iodide is pyridine alkaline, so that the Amberlyst 15 ion exchange resin and the 1-butyl-3-methylpyridine iodide can be highly combined together, namely, the hyaluronic acid slurry and the spinning solution can be well compatible, and the macroporous net structure of the Amberlyst 15 ion exchange resin enables the structure to be particularly stable; -SO contained in Amberlyst 15 ion exchange resin3H group, sodium hyaluronate A glucuronic acid containing hydroxyl, carboxyl, etc., thus making Amberlyst 15 ion exchange resin with H2O and sodium hyaluronate form a net structure by hydrogen bonds before, and then form a pseudo net structure with the raw material 1-butyl-3-methylpyridine iodide salt in the spinning solution, so that the mechanical property of the prepared fiber is improved.
Several specific examples of the present invention are given below, but the present invention is not limited by the examples.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1:
the raw materials of the hyaluronic acid fiber comprise, by weight, 12 parts of hyaluronic acid slurry and 88 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 0.8: 96.2: 3.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The preparation process of the spinning solution comprises the following steps: adding wool fibers, cotton fibers and ionic liquid into a high-pressure digestion tank, introducing helium for 25 minutes, reacting for 8 hours at 120 ℃, and then cooling to room temperature to obtain the spinning solution.
The preparation method of the 1-butyl-3-methylpyridine bromide salt comprises the following steps: 23.7g of pyridine and 55.2g of n-butyl iodide are respectively taken to be put into a flask to react for 4 hours at the temperature of 100 ℃, then the mixture is washed by ether and filtered, and finally the mixture is dried in vacuum at the temperature of 75 ℃ until the weight is constant to prepare the 1-butyl-3-methylpyridine bromide salt.
The preparation process of the hyaluronic acid slurry comprises the following steps: dissolving sodium hyaluronate in deionized water, stirring at room temperature until the sodium hyaluronate is completely dissolved to prepare a sodium hyaluronate aqueous solution, then adding an auxiliary agent into the sodium hyaluronate aqueous solution, and stirring at 75 ℃ for 2 hours to prepare hyaluronic acid slurry.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The preparation process of the auxiliary agent comprises the following steps: adding 50g of Amberlyst 15 ion exchange resin into a container, adding 250m L-0.25 mol/L silver nitrate aqueous solution into Amberlyst 15, uniformly mixing, carrying out ultrasonic treatment at room temperature for 20 minutes, standing for 12 hours, washing and filtering with deionized water and methanol respectively, and finally drying in a vacuum drying oven at 100 ℃ to constant weight to obtain the auxiliary agent.
The preparation process of the hyaluronic acid fiber comprises the following steps: and stirring and mixing the hyaluronic acid slurry and the spinning solution for 40 minutes to obtain mixed spinning solution, and then preparing the hyaluronic acid fiber according to a wet spinning process.
The wet spinning process is a conventional preparation process and comprises the following specific steps: adding the mixed spinning solution into an injector of a wet spinning machine, controlling the spinning speed to be 1.5mL/h by using a flow pump, spinning the spinning solution into distilled water at 60 ℃ under the conditions of 0.2MPa pressure and 115 ℃, naturally solidifying for 30s, and finally washing, oiling and drying to obtain the hyaluronic acid fiber.
The hyaluronic acid fiber is prepared by the following steps of: the fabric of the embodiment can be obtained through spinning, warping, sizing, denting, weaving, printing and dyeing, drying, shaping, carding, shearing and final shaping.
Example 2:
the raw materials of the hyaluronic acid fiber comprise, by weight, 4 parts of hyaluronic acid slurry and 96 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 2.3.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The preparation process of the spinning solution comprises the following steps: adding the wool fibers, the cotton fibers and the ionic liquid into a high-pressure digestion tank, introducing argon for 40 minutes, reacting for 12 hours at 80 ℃, and then cooling to room temperature to obtain the spinning solution.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The preparation process of the hyaluronic acid slurry comprises the following steps: dissolving sodium hyaluronate in deionized water, stirring at room temperature until the sodium hyaluronate is completely dissolved to prepare a sodium hyaluronate aqueous solution, then adding an auxiliary agent into the sodium hyaluronate aqueous solution, and stirring at 50 ℃ for 5 hours to prepare hyaluronic acid slurry.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The specific preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 3:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 2.5.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The preparation process of the spinning solution comprises the following steps: adding the wool fibers, the cotton fibers and the ionic liquid into a high-pressure digestion tank, introducing argon for 30 minutes, reacting for 10 hours at 100 ℃, and then cooling to room temperature to obtain the spinning solution.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The preparation process of the hyaluronic acid slurry comprises the following steps: dissolving sodium hyaluronate in deionized water, stirring at room temperature until the sodium hyaluronate is completely dissolved to prepare a sodium hyaluronate aqueous solution, then adding an auxiliary agent into the sodium hyaluronate aqueous solution, and stirring at 60 ℃ for 3 hours to prepare hyaluronic acid slurry.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 4:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 0.8.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The specific preparation process of the spinning dope was the same as in example 3.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 5:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 1.2.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
the raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The specific preparation process of the spinning dope was the same as in example 3.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 6:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 2.0.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The specific preparation process of the spinning dope was the same as in example 3.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 7:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 3.4.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
the raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The specific preparation process of the spinning dope was the same as in example 3.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 8:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serous fluid comprises the following raw materials of sodium hyaluronate and deionized water in a weight ratio of 1.2: 96.3.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The specific preparation process of the spinning dope was the same as in example 3.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 9:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 2.5.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1-butyl-3-methylpyridine iodide salt.
The specific preparation process of the spinning dope was the same as in example 3.
The specific preparation method of the 1-butyl-3-methylpyridine bromide salt is the same as that of example 1.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlite IRN160 ion exchange resin.
The preparation process of the auxiliary agent comprises the following steps: adding 50g of Amberlite IRN160 ion exchange resin into a container, adding 250m L-0.25 mol/L silver nitrate aqueous solution into the Amberlite IRN160 ion exchange resin, uniformly mixing, carrying out ultrasonic treatment at room temperature for 20 minutes, standing for 12 hours, washing with deionized water and methanol, filtering, and finally drying in a vacuum drying oven at 100 ℃ to constant weight to obtain the auxiliary agent.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
Example 10:
the raw materials of the hyaluronic acid fiber comprise, by weight, 8 parts of hyaluronic acid slurry and 92 parts of spinning stock solution.
The hyaluronic acid serum comprises the following raw materials of sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of 1.2: 96.3: 2.5.
the sodium hyaluronate is a mixture of macromolecular sodium hyaluronate, medium molecular sodium hyaluronate and small molecular sodium hyaluronate, and the weight ratio of the macromolecular sodium hyaluronate to the medium molecular sodium hyaluronate is 12: 35: 53.
wherein the macromolecular sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1800000-2200000D; the medium-molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 1000000-1800000D; the small molecule sodium hyaluronate refers to sodium hyaluronate with the molecular weight range of 400000-1000000D.
The raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, wherein the weight ratio of the wool fiber to the cotton fiber to the ionic liquid is 50: 15: 35.
the ionic liquid is 1, 3-dibutyl benzotriazole bromide.
The specific preparation process of the spinning dope was the same as in example 3.
The preparation method of the 1, 3-dibutyl benzotriazole bromide salt comprises the following steps: weighing 120g of benzotriazole (CAS: 95-14-7) and 175g of N-butyl bromide, heating and refluxing for reaction for 12 hours at 55 ℃ to obtain light yellow liquid N-butyl benzotriazole, adding 250g of N-butyl benzotriazole into a four-neck flask, slowly dropwise adding 81g of N-butyl bromide into the system, reacting for 72 hours at 70 ℃, washing a product after reaction by using ethyl acetate after the reaction is finished, and finally drying at 70 ℃ in a vacuum drying oven to constant weight to obtain the white solid 1, 3-dibutyl benzotriazole bromide salt.
The specific preparation process of the hyaluronic acid slurry is the same as that of example 3.
The auxiliary agent comprises the following raw materials: AgNO3Aqueous solution, Amberlyst 15 ion exchange resin.
The specific preparation process of the aid is the same as in example 1.
The preparation process of the hyaluronic acid fiber is the same as that of example 1.
The fabric of the embodiment can be obtained by the hyaluronic acid fiber according to the preparation process of the fabric in the embodiment 1.
The mechanical property of the hyaluronic acid fiber prepared by the concrete implementation of 1-10 in the invention is tested, and the test method refers to GB/T-24218.3-2010 test method for textile and non-woven fabrics part 3: determination of breaking strength and breaking elongation, the strength performance of the test samples is determined by adopting a FAVIMAT-BOBOBOT 2 full-automatic single fiber universal tester, the number of the test samples is not less than 30, the test average value is taken, and the test results are shown in Table 1:
TABLE 1
Figure BDA0002575756740000141
The content of hyaluronic acid in the fabric prepared in the specific examples 1-10 is measured by adopting a UV-Vis method, the content of hyaluronic acid in the fabric is measured after the fabric is washed for multiple times, and the test results are shown in Table 2:
TABLE 2
Figure BDA0002575756740000142

Claims (10)

1. The hyaluronic acid fiber is characterized in that raw materials comprise hyaluronic acid slurry and spinning solution.
2. The hyaluronic acid fiber of claim 1, wherein the raw materials of the hyaluronic acid fiber comprise, by weight, 4-12 parts of hyaluronic acid slurry and 88-96 parts of spinning solution.
3. The hyaluronic acid fiber of claim 1 or 2, wherein the hyaluronic acid slurry comprises sodium hyaluronate, deionized water and an auxiliary agent in a weight ratio of (0.8-2): (94.6-97.8): (0.8-3.4).
4. The hyaluronic acid fiber of claim 1 or 2, wherein the raw materials of the spinning solution comprise wool fiber, cotton fiber and ionic liquid, and the weight ratio of the wool fiber, the cotton fiber and the ionic liquid is 50: 15: 35;
the ionic liquid is selected from one or two of 1-butyl-4-methylmorpholine bromide, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylpyridine iodide, 1-butyl-3-methylpyridine bromide, 1, 3-dibutylbenzimidazole bromide and 1, 3-dibutylbenzotriazole bromide;
the preparation process of the spinning solution comprises the following steps: adding wool fibers, cotton fibers and ionic liquid into a high-pressure digestion tank, introducing inert gas for 25-40 minutes, reacting for 8-12 hours at 80-120 ℃, and then cooling to room temperature to obtain spinning stock solution;
the inert gas is selected from helium, neon and argon.
5. The hyaluronic acid fiber of claim 4, wherein the ionic liquid is 1-butyl-3-methylpyridine bromide.
6. The preparation method of the hyaluronic acid fiber according to claim 3, wherein the preparation process of the hyaluronic acid fiber comprises the following steps: and stirring and mixing the hyaluronic acid slurry and the spinning stock solution for 40-60 minutes to obtain a mixed spinning solution, and then preparing the hyaluronic acid fiber according to a wet spinning process.
7. The method for preparing hyaluronic acid fiber according to claim 6, wherein the hyaluronic acid slurry is prepared by the following steps:
dissolving sodium hyaluronate in deionized water, stirring at room temperature until the sodium hyaluronate is completely dissolved to obtain a sodium hyaluronate aqueous solution, adding an auxiliary agent into the sodium hyaluronate aqueous solution, and stirring at 50-75 ℃ for 2-5 hours to obtain hyaluronic acid slurry.
8. The preparation method of hyaluronic acid fiber according to claim 7, wherein the auxiliary agent comprises the following raw materials: AgNO3Aqueous solutions, ion exchange resins;
the ion exchange resin is selected from one of Amberlite IRN160 ion exchange resin, Amberlyst 15 ion exchange resin, Amberlite200CNa ion exchange resin and AMBERLITE IR120 Na ion exchange resin;
the preparation process of the auxiliary agent comprises the following steps: adding 50g of ion exchange resin into a container, adding 250m L-0.25 mol/L silver nitrate aqueous solution into the ion exchange resin, uniformly mixing, performing ultrasonic treatment at room temperature for 20 minutes, standing for 12 hours, washing and filtering with deionized water and methanol respectively, and finally drying in a vacuum drying oven at 100 ℃ to constant weight to obtain the auxiliary agent.
9. The method of claim 8, wherein the ion exchange resin is Amberlyst 15.
10. Use of a hyaluronic acid fiber according to any of claims 1-5, wherein said hyaluronic acid fiber is used in textile fabrics.
CN202010653233.7A 2020-07-08 2020-07-08 Hyaluronic acid fiber and preparation method and application thereof Withdrawn CN111621873A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112094419A (en) * 2020-09-16 2020-12-18 青岛迦南美地家居用品有限公司 Hyaluronic acid microcapsule, fiber containing hyaluronic acid microcapsule, preparation method and application
CN112226836A (en) * 2020-10-15 2021-01-15 深圳千维生态纺织有限公司 Chamomile fiber containing blue fragrant oil azulene and capable of promoting sleep and beautifying features and preparation method of chamomile fiber
CN114481350A (en) * 2022-03-09 2022-05-13 青岛迦南美地家居用品有限公司 Hyaluronic acid acrylic fiber and preparation method thereof
CN114736316A (en) * 2022-04-22 2022-07-12 山东安华生物医药股份有限公司 Environment-friendly preparation method and application of acetylated hyaluronate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112094419A (en) * 2020-09-16 2020-12-18 青岛迦南美地家居用品有限公司 Hyaluronic acid microcapsule, fiber containing hyaluronic acid microcapsule, preparation method and application
CN112226836A (en) * 2020-10-15 2021-01-15 深圳千维生态纺织有限公司 Chamomile fiber containing blue fragrant oil azulene and capable of promoting sleep and beautifying features and preparation method of chamomile fiber
CN114481350A (en) * 2022-03-09 2022-05-13 青岛迦南美地家居用品有限公司 Hyaluronic acid acrylic fiber and preparation method thereof
CN114736316A (en) * 2022-04-22 2022-07-12 山东安华生物医药股份有限公司 Environment-friendly preparation method and application of acetylated hyaluronate

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