CN102628219A - Preparation method of functional fiber grafted with multilayered hydrogel - Google Patents

Abstract

The invention provides a preparation method of functional fiber grafted with multilayer hydrogel. The preparation method is as follows: first, use ultraviolet radiation to graft sodium polyacrylate on the surface of the fiber, then immerse the fiber in a certain concentration of sodium alginate aqueous solution containing water-soluble polymer additives, and scrape off the surface of the fiber with a scraper after taking it out Excessive adhesion solution, and finally immersed in calcium chloride solution to cross-link to prepare functionalized fibers grafted with the first layer of hydrogel. The functionalized fibers were washed with deionized water, re-immersed in the mixed aqueous solution of water-soluble polymer additives and sodium alginate, and then cross-linked again with calcium chloride solution to obtain the functionalized fibers of the grafted second layer of hydrogel. fiber. By analogy, functionalized fibers grafted with multilayer hydrogels were prepared.

Description

A preparation method of functional fiber grafted with multilayer hydrogel

technical field

The invention relates to a preparation method of a functionalized fiber grafted with multilayer hydrogel, belonging to the field of functional polymers.

Background technique

Hydrogel is a water-swellable cross-linked polymer that can absorb a large amount of water without dissolving in water, and has good softness, elasticity, water storage capacity and biocompatibility. Hydrogels can respond to stimuli and have reversible swelling behavior, and can exhibit adjustable intelligent swelling behavior in response to external stimuli such as pH value, temperature, ionic strength, and electric field. Therefore, research on hydrogels has become a research hotspot in the fields of materials science, biology, and medicine. In recent years, the study of a novel polysaccharide-based multilayer membrane hydrogel as a biofunctional carrier has attracted the interest of researchers. Ladet et al. prepared a multilayer membrane hydrogel [Multi-membrane hydrogels.Nature, 2008, 452, 76-79] for the first time. The preparation process is to control the gradual assembly of chitosan or sodium alginate from the outside to the inside. The dynamic gelation process is realized. This brand-new multi-layer advanced structure breaks through the shortcomings of the single structure of traditional homogeneous hydrogels, and further broadens the application range of hydrogels, such as: co-cultivation of multi-cells, evaluation of cell-cell interactions and advanced Mode of drug delivery.

Alginate is a natural polysaccharide extracted from brown algae, consisting of two structures: D-mannuronic acid residue (dissociation constant pKa=3.38) and L-guluronic acid residue (pKa=3.65) Single unit composition. Sodium alginate is a product produced by the action of alginic acid and alkali. It is milky white, soluble in water, and does not solidify when boiled or cooled. Sodium alginate aqueous solution meets Ca2+ to form cross-linked calcium alginate hydrogel, which has good biodegradability and biocompatibility. Based on the rapid gelation reaction of sodium alginate and divalent cations, Dai Hongjun successfully prepared the onion-like structure calcium alginate multilayer hydrogel by the method of dynamic self-assembly, using the spherical gel core as a template to gradually react from the inside to the outside. Glue, and studied the pulse release properties of the multilayer hydrogel for drugs [Multi-membrane Hydrogel Fabricated by Facile Dynamic Self-assembly, Matter, 2009, 5, 1987-1989]. The preparation method has fast response, simple operation, no need for acid, alkali or organic solvent, and can control the preparation process, thereby adjusting the thickness of the gel film and the size of the gap between layers, and can adjust the loading of the target in practical applications. Intake and microenvironment. However, pure calcium alginate hydrogel is easy to swell and become brittle, and has a large volume shrinkage after drying, while the above-mentioned multilayer film hydrogel is prepared based on the core of calcium alginate microspheres. , tissue engineering and other applications that require a certain strength are limited.

The fiber material has good flexibility and mechanical strength, can be prepared into various shapes, and is convenient to use. But the materials that can be spun into fibers are very limited, and the formed fibers often lack various functionalities. Zhao Kongyin et al. prepared a calcium ion cross-linked grafted polymer hydrogel fiber material, combining the good flexibility of the fiber material with the adjustable intelligent swelling behavior of the hydrogel [201010576349.1]. However, the above-mentioned patent uses gamma ray radiation when preparing the fiber material grafted with sodium polyacrylate, which causes damage to the fiber matrix, and the material cannot achieve pulse-controlled release of the drug.

This patent adopts the method of ultraviolet radiation to graft sodium polyacrylate on the fiber surface, then immerse the fiber in a certain concentration of sodium alginate aqueous solution, take it out, scrape off the solution on the fiber surface with a scraper, and finally immerse it in calcium chloride solution Intermediate crosslinking to prepare functionalized fibers grafted with the first layer of hydrogel. Rinse the functionalized fibers with deionized water, re-immerse them in the mixed aqueous solution of water-soluble polymer additives and sodium alginate, and then cross-link again with calcium chloride solution to obtain the functionalized fibers grafted with the second layer of hydrogel fiber. By analogy, the preparation of functional fibers grafted with multilayer hydrogels has not been reported at home and abroad.

Contents of the invention

In view of the deficiencies in the prior art, the technical problem to be solved by the present invention is that the pure calcium alginate hydrogel has low strength, is easy to swell and become brittle, has a large volume shrinkage after drying, and the fiber-grafted single-layer hydrogel does not have pulse release performance issues.

The technical solution of the present invention to solve the above-mentioned technical problems is to prepare a functionalized fiber grafted with multi-layer hydrogel.

The invention provides a method for preparing functional fibers grafted with multilayer hydrogel, which is characterized in that the preparation steps are as follows:

a) Put the fibers into an acrylic acid aqueous solution with a volume percentage of 1% to 50%, add a polymerization inhibitor ferrous ammonium sulfate with a mass percentage concentration of 0.5 to 3%, and pass in nitrogen for protection. Irradiate with ultraviolet light for 0.2 to 1 hour, take it out and rinse with water for 3 to 5 times to remove unreacted monomers and homopolymers to obtain fibers grafted with polyacrylic acid, and then use hydrogen with a concentration of 1% to 10% by mass Sodium oxide aqueous solution is neutralized, obtains the fiber of sodium polyacrylate graft;

b) Prepare a mixed aqueous solution of sodium alginate with a mass percentage concentration of 0.2% to 8% and a water-soluble polymer additive with a mass percentage concentration of 0 to 10%, and let it stand for defoaming before use; at the same time, prepare a mass percentage concentration of 1 %～10% calcium chloride aqueous solution;

c) The fibers of grafted sodium polyacrylate obtained in step a) are completely immersed in the mixed aqueous solution of water-soluble polymer additives and sodium alginate for 0.5 to 2 hours, drip for 2 to 5 minutes after taking it out, and scrape off the adhesion with a scraper Too much viscous solution, so that the attachment liquid on the surface of the fiber is as uniform as possible, immediately put it into the calcium chloride aqueous solution prepared in step b), cross-link for 0.5 to 2 hours, and obtain the function of grafting the first layer of hydrogel chemical fiber;

d) Rinse the functionalized fiber grafted with the first layer of hydrogel obtained in step c) for 2 to 3 times with deionized water, and re-immerse it in the mixture of the water-soluble polymer additive prepared in step b) and sodium alginate 0.5 to 2 hours in the aqueous solution, take it out and drip for 2 to 5 minutes, scrape off the excessive viscous solution with a scraper, make the adhesion liquid on the surface of the fiber as uniform as possible, and immediately put it into the chlorinated solution prepared in step b). In the calcium aqueous solution, cross-link for 0.5 to 2 hours to obtain the functional fiber grafted with the second layer of hydrogel;

e) Repeatedly immerse the functionalized fibers grafted with the second layer of hydrogel obtained in step d) into the mixed aqueous solution of water-soluble polymer additives and sodium alginate, refer to step c) and cross-link through calcium chloride aqueous solution to obtain the grafted fiber The functionalized fibers of the third layer of hydrogel are grafted, and so on, to obtain the functionalized fibers of the fourth layer, the fifth layer, and the 20th layer of hydrogel.

The fiber matrix described in the present invention includes polyamide, polypropylene, polyethylene, polytetrafluoroethylene, polyacrylonitrile and polysulfone. The form of the fiber includes monofilament fiber, non-woven fabric, tow and hollow fiber. The water-soluble polymer additive includes hydroxypropyl methylcellulose, carboxymethyl chitosan, water-soluble starch, polyethylene glycol, polyacrylic acid, polyacrylamide and polyvinylpyrrolidone.

The functionalized fiber described in the present invention is contained by multi-layer hydrogel, wherein, the first layer of hydrogel is grafted on the fiber matrix by means of calcium ion cross-linking, the second layer of hydrogel wraps the fiber and the second layer of hydrogel One layer of hydrogel, the third layer of hydrogel wrapped fiber, the first layer and the second layer of hydrogel, the Nth layer of hydrogel wrapped fiber and the first layer, the second layer... until the N-1th layer layer hydrogel, where 3≤N≤20.

The preparation process of the present invention is simple and easy, and the obtained functional fiber grafted with multi-layer hydrogel has good toughness and biocompatibility, and the swelling degree of the multi-layer hydrogel grafted on the fiber can be increased by adding The functionalized fiber can be used in adsorption separation, drug controlled release, immobilized enzyme, tissue engineering, catalysis and other fields.

Detailed ways

The specific embodiments of the present invention are introduced below, but the present invention is not limited by the embodiments.

Example 1. A preparation method of polypropylene fiber non-woven fabric grafted with five layers of calcium alginate hydrogel

Put the polypropylene fiber non-woven fabric into the acrylic acid aqueous solution with a volume percentage of 50%, add a polymerization inhibitor ferrous ammonium sulfate with a mass percentage concentration of 3%, pass through nitrogen for protection, and irradiate with a 500W ultraviolet lamp at room temperature After taking it out for 0.2 hours, rinse it with deionized water for 3 to 5 times to remove unreacted monomers and homopolymers to obtain a polypropylene fiber nonwoven fabric grafted with acrylic acid. Then it is neutralized with an aqueous sodium hydroxide solution with a concentration of 10% by mass to obtain a polypropylene fiber nonwoven fabric grafted with sodium polyacrylate.

An aqueous solution of sodium alginate with a concentration of 0.2% by mass was prepared, and was left to stand for defoaming before use; at the same time, an aqueous solution of calcium chloride with a concentration of 1% by mass was prepared. Cut the polypropylene fiber non-woven fabric into a size of 10mm×10mm square, completely immerse it in the sodium alginate aqueous solution for 0.5 hours, take it out and drip it for 2 minutes, scrape off the excessive viscous solution adhered with a scraper, and make the fibers The attachment liquid on the surface was as uniform as possible, and immediately put it into the calcium chloride aqueous solution, and cross-linked for 1 hour to obtain the polypropylene fiber non-woven fabric grafted with the first layer of calcium alginate hydrogel.

Rinse the polypropylene fiber non-woven fabric grafted with the first layer of hydrogel 2 to 3 times with deionized water, re-immerse it in the aqueous solution of sodium alginate for 0.5 hours, take it out, drip it for 2 minutes, and scrape it off with a scraper. Adhesive too much viscous solution, make the attachment liquid on the surface of the fiber as uniform as possible, immediately put it into the calcium chloride aqueous solution, crosslink for 0.5 hours, and obtain the polypropylene fiber non-woven fabric grafted with the second layer of hydrogel . The polypropylene fiber non-woven fabric grafted with the second layer of hydrogel is repeatedly immersed in the solution of sodium alginate, cross-linked by calcium chloride aqueous solution to obtain the fiber grafted with the third layer of hydrogel, and so on, to obtain Polypropylene fiber nonwovens grafted with five layers of calcium alginate hydrogel.

Example 2. A preparation method of a polypropylene fiber non-woven fabric grafted with five layers of polyacrylic acid/calcium alginate hydrogel

Put the polypropylene fiber non-woven fabric into the acrylic acid aqueous solution with a volume percentage of 50%, add a polymerization inhibitor ferrous ammonium sulfate with a mass percentage concentration of 3%, pass through nitrogen for protection, and irradiate with a 500W ultraviolet lamp at room temperature After 0.2 hours, take it out and wash it with water for 3 to 5 times to remove unreacted monomers and homopolymers to obtain a polypropylene fiber non-woven fabric grafted with acrylic acid. After neutralizing with a 10% sodium hydroxide aqueous solution, A polypropylene fiber nonwoven fabric grafted with sodium polyacrylate was obtained.

Prepare a mixed aqueous solution of sodium alginate with a concentration of 0.2% by mass and polyacrylic acid with a concentration of 1% by mass, and let it stand for defoaming before use; at the same time, prepare an aqueous solution of calcium chloride with a concentration of 1% by mass. Cut the polypropylene fiber non-woven fabric into a size of 10mm×10mm square, completely immerse it in the mixed aqueous solution of polyacrylic acid and sodium alginate for 0.5 hours, take it out and drip it for 2 minutes, and scrape off the excessive adhesion with a scraper. Thick solution, so that the attachment liquid on the surface of the fiber is as uniform as possible, immediately put it into the calcium chloride aqueous solution, and cross-link for 0.5 hours to obtain the polypropylene fiber non-woven fabric grafted with the first layer of polyacrylic acid/calcium alginate hydrogel .

Rinse the polypropylene fiber non-woven fabric grafted with the first layer of hydrogel 2 to 3 times with deionized water, re-immerse it in the mixed aqueous solution of polyacrylic acid and sodium alginate for 0.5 hours, take it out and drip it for 2 minutes , use a spatula to scrape off the excessive viscous solution attached to the surface of the fiber to make the attachment liquid on the surface of the fiber as uniform as possible, immediately put it into an aqueous calcium chloride solution, and cross-link for 0.5 hours to obtain the polymer grafted with the second layer of hydrogel. Acrylic non-woven fabric. The polypropylene fiber non-woven fabric grafted with the second layer of hydrogel was repeatedly immersed in the mixed aqueous solution of polyacrylic acid and sodium alginate, and cross-linked by calcium chloride aqueous solution to obtain the fibers grafted with the third layer of hydrogel. By analogy, a polypropylene fiber nonwoven fabric grafted with five layers of polyacrylic acid/calcium alginate hydrogel was obtained.

Example 3. A preparation method of polypropylene fiber monofilament grafted with five layers of polyethylene glycol/calcium alginate hydrogel

Put the polypropylene fiber monofilament into the acrylic acid aqueous solution of 10% by volume, add the polymerization inhibitor ferrous ammonium sulfate with a concentration of 0.5% by mass, feed nitrogen for protection, and irradiate 0.5% with a 500W ultraviolet lamp at room temperature. hours, take it out and rinse with water for 3 to 5 times to remove unreacted monomers and homopolymers to obtain polypropylene fiber monofilaments grafted with acrylic acid, which are neutralized with 5% sodium hydroxide aqueous solution to obtain poly Sodium acrylate grafted polypropylene fiber monofilament.

Prepare a mixed aqueous solution of sodium alginate with a concentration of 1% by mass and polyethylene glycol with a concentration of 1% by mass, and let it stand for defoaming before use; at the same time, prepare an aqueous solution of calcium chloride with a concentration of 2% by mass. Cut the polypropylene fiber monofilament into a size of 10mm, disperse the monofilament fiber and completely immerse it in the mixed aqueous solution of polyethylene glycol and sodium alginate for 0.5 hours, take it out and drip it for 2 minutes, scrape off the adhered Too much viscous solution to make the attachment liquid on the fiber surface as uniform as possible, immediately put it into the calcium chloride aqueous solution, and crosslink for 1 hour to obtain the polypropylene fiber monofilament grafted with the first layer of hydrogel.

Rinse the polypropylene fiber monofilament grafted with the first layer of hydrogel 2 to 3 times with deionized water, re-immerse it in the mixed aqueous solution of polyethylene glycol and sodium alginate for 0.5 hours, take it out and drip it for 2 minutes, Use a scraper to scrape off the excessive viscous solution attached to make the attachment liquid on the surface of the fiber as uniform as possible, immediately put it into the calcium chloride aqueous solution, and cross-link for 1 hour to obtain the polypropylene grafted with the second layer of hydrogel fiber monofilament. The polypropylene fiber monofilament grafted with the second layer of hydrogel was repeatedly immersed in the mixed aqueous solution of polyethylene glycol and sodium alginate, and cross-linked by calcium chloride aqueous solution to obtain the fiber grafted with the third layer of hydrogel. By analogy, a polypropylene fiber monofilament grafted with five layers of polyethylene glycol/calcium alginate hydrogel is obtained.

Example 4. A preparation method of a polysulfone hollow fiber grafted with five layers of carboxymethyl chitosan/calcium alginate hydrogel

Put the polysulfone hollow fiber into 10% by volume of acrylic acid aqueous solution, add a polymerization inhibitor ferrous ammonium sulfate with a concentration of 0.5% by mass, pass through nitrogen as a protection, and irradiate with a 500W ultraviolet lamp for 0.5 hours at room temperature After taking it out, rinse it with water for 3 to 5 times to remove unreacted monomers and homopolymers to obtain a polysulfone hollow fiber grafted with acrylic acid, and then neutralize it with an aqueous sodium hydroxide solution with a concentration of 10% by mass to obtain polyacrylic acid Sodium grafted polysulfone hollow fibers.

Prepare a mixed aqueous solution of sodium alginate with a mass percentage concentration of 0.75% and a mass percentage concentration of 0.5% carboxymethyl chitosan, stand for defoaming and stand-by; prepare a calcium chloride aqueous solution with a mass percentage concentration of 5% at the same time . Cut the polysulfone hollow fiber into a size of 10mm, disperse the polysulfone hollow fiber and completely immerse it in the mixed aqueous solution of carboxymethyl chitosan and sodium alginate for 0.5 hours, take it out, drip for 5 minutes, and scrape it off with a scraper Adhesive too much viscous solution, make the attachment liquid on the fiber surface as uniform as possible, immediately put it into calcium chloride aqueous solution, crosslink for 1 hour, and obtain the first layer of grafted carboxymethyl chitosan/calcium alginate water Gel polysulfone hollow fibers.

Rinse the polysulfone hollow fiber grafted with the first layer of hydrogel 2 to 3 times with deionized water, re-immerse it in the mixed aqueous solution of carboxymethyl chitosan and sodium alginate for 0.5 hours, take it out and drip for 2 Minutes, scrape off the excessive viscous solution with a scraper to make the adhesion liquid on the surface of the fiber as uniform as possible, immediately put it into the calcium chloride aqueous solution, crosslink for 1 hour, and obtain the grafted second layer of hydrogel Polysulfone hollow fiber. The polysulfone hollow fiber grafted with the second layer of hydrogel is repeatedly immersed in the mixed aqueous solution of carboxymethyl chitosan and sodium alginate, and cross-linked by calcium chloride aqueous solution to obtain the fiber grafted with the third layer of hydrogel , and so on, a polysulfone hollow fiber grafted with five layers of carboxymethyl chitosan/calcium alginate hydrogel was obtained.

Example 5. A preparation method of a polyacrylonitrile hollow fiber grafted with five layers of hydroxypropyl methylcellulose/calcium alginate hydrogel

Put the polyacrylonitrile hollow fiber into the acrylic acid aqueous solution with a volume percentage of 20%, add a polymerization inhibitor ferrous ammonium sulfate with a mass percentage concentration of 3%, pass through nitrogen as a protection, and irradiate 0.5 with a 500W ultraviolet lamp at room temperature. After taking it out, rinse it with deionized water for 3 to 5 times to remove unreacted monomers and homopolymers to obtain polyacrylonitrile hollow fibers grafted with acrylic acid, and then use 10% sodium hydroxide aqueous solution to Neutralize to obtain polyacrylonitrile hollow fibers grafted with sodium polyacrylate.

Prepare a mixed aqueous solution of sodium alginate with a mass percentage concentration of 0.75% and a mass percentage concentration of 0.5% hydroxypropyl methylcellulose, and stand for defoaming; prepare calcium chloride with a mass percentage concentration of 5% at the same time aqueous solution. Cut the polyacrylonitrile hollow fiber into a size of 10mm, disperse the polyacrylonitrile hollow fiber and completely immerse it in the mixed aqueous solution of hydroxypropyl methylcellulose and sodium alginate for 0.5 hours, take it out and drip it for 5 minutes, and use Scrape off the excessive viscous solution attached to the scraper to make the attachment liquid on the surface of the fiber as uniform as possible, immediately put it into the calcium chloride aqueous solution, and crosslink for 2 hours to obtain the first layer of grafted hydroxypropyl methylcellulose/ Polyacrylonitrile hollow fibers in calcium alginate hydrogels.

Rinse the polyacrylonitrile hollow fiber grafted with the first layer of hydrogel 2 to 3 times with deionized water, re-immerse it in the mixed aqueous solution of hydroxypropyl methylcellulose and sodium alginate for 0.5 hours, take it out and drop Drip for 2 minutes, scrape off the excessive viscous solution with a scraper, make the adhesion liquid on the surface of the fiber as uniform as possible, immediately put it into the calcium chloride aqueous solution, and cross-link for 2 hours to obtain the second layer of grafted hydraulic gel. Glue polyacrylonitrile hollow fibers. The polyacrylonitrile hollow fiber grafted with the second layer of hydrogel is repeatedly immersed in the mixed aqueous solution of hydroxypropyl methylcellulose and sodium alginate, and cross-linked by calcium chloride aqueous solution to obtain the grafted third layer of hydrogel By analogy, the polyacrylonitrile hollow fiber grafted with five layers of hydroxypropyl methylcellulose/calcium alginate hydrogel was obtained.

Claims (5)

1. A preparation method of a functionalized fiber grafted with multilayer hydrogel, characterized in that it may further comprise the steps: a) Put the fiber into an acrylic acid aqueous solution with a volume percentage of 1% to 50%, add a polymerization inhibitor ferrous ammonium sulfate with a mass percentage concentration of 0.5 to 3%, feed nitrogen for protection, and use a 500W ultraviolet light at room temperature Irradiate the lamp for 0.2-1 hour, take it out and wash it with water for 3-5 times to remove unreacted monomers and homopolymers to obtain polyacrylic acid grafted fibers, and then use sodium hydroxide with a mass percentage concentration of 1%-10% The aqueous solution is neutralized to obtain fibers grafted by sodium polyacrylate; b) Prepare a mixed aqueous solution of sodium alginate with a mass percentage concentration of 0.2% to 8% and a water-soluble polymer additive with a mass percentage concentration of 0 to 10%, and let it stand for defoaming before use; at the same time, prepare a mass percentage concentration of 1 %～10% calcium chloride aqueous solution; c) The fibers of grafted sodium polyacrylate obtained in step a) are completely immersed in the mixed aqueous solution of water-soluble polymer additives and sodium alginate for 0.5 to 2 hours, drip for 2 to 5 minutes after taking it out, and scrape off the adhesion with a scraper Too much viscous solution, so that the attachment liquid on the surface of the fiber is as uniform as possible, immediately put it into the calcium chloride aqueous solution prepared in step b), cross-link for 0.5 to 2 hours, and obtain the function of grafting the first layer of hydrogel chemical fiber; d) Rinse the functionalized fiber grafted with the first layer of hydrogel obtained in step c) for 2 to 3 times with deionized water, and re-immerse it in the mixture of the water-soluble polymer additive prepared in step b) and sodium alginate 0.5 to 2 hours in the aqueous solution, take it out and drip for 2 to 5 minutes, scrape off the excessive viscous solution with a scraper, make the adhesion liquid on the surface of the fiber as uniform as possible, and immediately put it into the chlorinated solution prepared in step b). In the calcium aqueous solution, cross-link for 0.5 to 2 hours to obtain the functional fiber grafted with the second layer of hydrogel; e) Repeatedly immerse the functionalized fibers grafted with the second layer of hydrogel obtained in step d) into the mixed aqueous solution of water-soluble polymer additives and sodium alginate, refer to step c) and cross-link through calcium chloride aqueous solution to obtain the grafted fiber The functionalized fibers of the third layer of hydrogel are grafted, and so on, the functionalized fibers of the fourth layer, the fifth layer, and the 20th layer of hydrogel are obtained. 2. the preparation method of the functionalization fiber of a kind of graft multilayer hydrogel as claimed in claim 1, it is characterized in that described fiber matrix comprises polyamide, polypropylene, polyethylene, polytetrafluoroethylene, poly Acrylonitrile and polysulfone. 3. The preparation method of a functional fiber grafted with multilayer hydrogel as claimed in claim 1, characterized in that the shape of the fiber comprises monofilament fiber, non-woven fabric, tow and hollow fiber. 4. the preparation method of the functionalization fiber of a kind of graft multilayer hydrogel as claimed in claim 1, it is characterized in that described water-soluble polymer additive comprises hydroxypropyl methylcellulose, carboxymethyl shell Polysaccharides, water soluble starch, polyethylene glycol, polyacrylic acid, polyacrylamide and polyvinylpyrrolidone. 5. a kind of preparation method of the functionalized fiber of grafting multilayer hydrogel as claimed in claim 1, it is characterized in that described functionalized fiber is comprised by multilayer hydrogel, the first layer of hydrogel Relying on calcium ion cross-linking and grafting on the fiber matrix, the second layer of hydrogel wraps the fiber and the first layer of hydrogel, the third layer of hydrogel wraps the fiber, the first layer and the second layer of hydrogel, N A layer of hydrogel wraps the fiber and the first layer, the second layer... until the N-1th layer of hydrogel, wherein 3≤N≤20.