CN117626471B - A continuous preparation method for high-strength and tough ion-conducting hydrogel fibers - Google Patents
A continuous preparation method for high-strength and tough ion-conducting hydrogel fibersInfo
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- CN117626471B CN117626471B CN202311421548.9A CN202311421548A CN117626471B CN 117626471 B CN117626471 B CN 117626471B CN 202311421548 A CN202311421548 A CN 202311421548A CN 117626471 B CN117626471 B CN 117626471B
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
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- D01F1/10—Other agents for modifying properties
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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Abstract
本发明公开了一种高强韧离子导电水凝胶纤维的连续化制备方法，采用湿法纺丝连续规模化制备高度取向的聚乙烯醇/海藻酸钠/硼砂复合水凝胶纤维，该水凝胶纤维具有互锁双网络结构，以刚性的硼砂交联海藻酸钠作为第一网络，通过冷冻解冻构筑的物理交联聚乙烯醇作为第二网络，两网络之间通过硼砂进一步交联，大幅提高水凝胶的力学性能，同时负电荷的海藻酸钠促进离子传输。本发明制备的水凝胶纤维具有优异的力学性能、较高的离子导电性以及良好的生物相容性，在柔性可穿戴器件领域具有良好的应用前景。
This invention discloses a continuous preparation method for high-strength and tough ion-conductive hydrogel fibers. Highly oriented polyvinyl alcohol/sodium alginate/borax composite hydrogel fibers are prepared on a continuous, large-scale basis using wet spinning. These hydrogel fibers possess an interlocking dual-network structure. A rigid borax-crosslinked sodium alginate forms the first network, while physically crosslinked polyvinyl alcohol, constructed through freeze-thaw cycles, forms the second network. The two networks are further crosslinked by borax, significantly improving the mechanical properties of the hydrogel. Simultaneously, the negatively charged sodium alginate promotes ion transport. The hydrogel fibers prepared by this invention exhibit excellent mechanical properties, high ion conductivity, and good biocompatibility, showing promising application prospects in the field of flexible wearable devices.
Description
Technical Field
The invention relates to the technical field of hydrogel fiber materials, in particular to a continuous preparation method of high-strength and high-toughness ion conductive hydrogel fibers.
Background
The flexible wearable electronic equipment has the advantages of unique flexibility, ductility and the like, and has wide application prospects in the fields of information, medical treatment, energy sources and the like. The flexible electronic device is not only capable of adapting to irregular surfaces, but also has good air and moisture permeability, which is difficult to realize by the thin film type electronic device, because of direct or indirect close contact with the skin. The telescopic conductive fiber is an important component of next-generation flexible wearable electronic equipment, and compared with traditional film material equipment, the wearable electronic equipment based on fiber or textile can be assembled on clothes through modern weaving processes such as weaving, knitting, embroidery and the like, so that the problem of poor air permeability and moisture permeability of the film material equipment is solved, and the wearable requirement can be better met.
The existing conductive fibers are mostly conductive through electrons, have the limitations of poor ductility, opacity, poor biocompatibility and the like, and the conductivity can be rapidly reduced during stretching. The ion conductive hydrogel fiber has excellent biocompatibility, softness and higher ion conductivity and ductility, and is expected to play an important role in the field of flexible wearable electronic devices.
However, hydrogels and their precursor solutions are poorly spinnable, which makes it difficult to achieve mass production of ion-conductive hydrogel fibers by continuous spinning. Wet spinning is an efficient fiber preparation process, but conventional wet spinning processes are a non-solvent induced phase separation process of thermoplastic polymers, which is not suitable for the preparation of covalently crosslinked fibers. Since the crosslinking reaction is usually carried out in an unstressed state and this is a time-consuming process, but spinning is a dynamic process carried out under the action of drawing forces. Thus, most of the covalently crosslinked hydrogel fibers previously reported were prepared using tubular molds. Part of research works adopt wet spinning or dry spinning to prepare hydrogel fibers, but the prepared hydrogel fibers are of a single-network physical crosslinking structure, and have the problems of poor mechanical properties, low fatigue resistance stability, insufficient functionality and the like. Therefore, a continuous large-scale preparation method of high-strength, large-deformation elongation and high-conductivity hydrogel fibers is needed.
At present, the preparation method of the one-dimensional hydrogel fiber mainly comprises wet spinning and dry-wet spinning. For example, the Chinese patent (CN 105040153B) adopts wet spinning combined with ultraviolet light to initiate free radical polymerization reaction, and prepares the intelligent hydrogel fiber with double temperature response. The article ：Bioinspiredultra-stretchable and anti-freezing conductive hydrogel fibers with ordered and reversible polymer chain alignment, published in the Nature Communications journal by Ma et al reports a high performance and low cost elastic stretchable conductive hydrogel fiber useful for developing stretchable electronics based on textile materials. Yun et al, journal ADVANCED MATERIALS, highly stretchable, STRAIN SENSING hydrogel optical fibers, filled an aqueous solution of a crosslinking agent, initiator and monomer into a silicone tube mold and crosslinked in ultraviolet radiation under the protection of nitrogen at 50 ℃ to obtain covalently crosslinked hydrogel fibers. Ran et al, journal of CHEMICAL ENGINEERING, high-strength, highly conductive and woven organic hydrogel fibers for flexible electronics, foam-removing the mixed solution of polyvinyl alcohol and temperature sensitive particles, injecting into PVC tube, and repeatedly freeze thawing for 3 times to obtain High strength, high conductivity and woven organic hydrogel fiber. None of the above methods effectively continuously produce hydrogel fibers.
The article Wearable androbustpolyimide hydrogel fiber textiles for strain sensors by Zhang et al, published in ACSAPPLIED MATERIALS & Interfaces journal, uses an aqueous solution of calcium chloride as a coagulation bath to prepare polyimide hydrogel fibers by continuous wet spinning, which exhibit excellent chemical stability. Chinese patent (CN 104652119A) discloses a double-network hydrogel fiber prepared by combining natural polysaccharide and acrylamide polymer through wet spinning, dry-wet spinning or gel spinning with radiation crosslinking. The Chinese patent (CN 115287777A) adopts a wet spinning method to utilize chemical crosslinking and the same physical crosslinking mode to modify the poly-dopamine-modified poly-pyrrole-poly-vinyl alcohol high-strength self-healing conductive hydrogel fiber. The fiber has the highest tensile strength of 2.54MPa, the elongation at break of 500 percent and the conductivity of 0.71Sm -1, and has good water-retaining and freezing-resisting capabilities. The article ：Stretchable,self-healing,conductive hydrogel fibers for strain sensing and triboelectric energy-harvesting smart textiles, by Wang et al, journal of Nano Energy, uses the thermoreversible sol-gel transition properties of physically cross-linked poly (N-acryloylglycinamide-acrylamide) (PNA) hydrogels to prepare a stretchable, electrically conductive and self-healing hydrogel fiber using continuous dry-wet spinning. The fiber has the highest tensile strength of 2.27MPa, the elongation at break of 900 percent and the electrical conductivity of 0.69S m -1, and has good self-repairing capability.
Disclosure of Invention
The invention aims to solve the problems that the existing hydrogel fiber has poor mechanical properties and is difficult to realize large-scale preparation through continuous spinning, and provides a continuous preparation method of the high-strength and high-deformation elongation and high-conductivity hydrogel fiber, so that the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber with excellent mechanical properties and ion conductivity is obtained, and is widely applied to the field of intelligent sensing.
The technical scheme is that the continuous preparation method of the high-strength and high-toughness ion conductive hydrogel fiber comprises the following steps:
1) The preparation of raw materials comprises the steps of taking a certain amount of polyvinyl alcohol particles, adding deionized water, dissolving for 2 hours at 90 ℃ to obtain a polyvinyl alcohol solution, adding sodium alginate powder into the deionized water while stirring, standing for 3 hours, and continuing stirring for 2 hours after the sodium alginate is fully swelled to obtain a sodium alginate solution;
2) Adding the sodium alginate solution obtained in the step 1) into the polyvinyl alcohol solution obtained in the step 1), adding a certain amount of borax while stirring, stirring at 90 ℃ for 2 hours, obtaining a mixed solution after complete dissolution, and centrifuging and defoaming the mixed solution at a low speed to obtain the spinning solution;
3) Extruding the spinning solution obtained in the step 2) through a needle head of an injector, and solidifying and forming the formed silk by a coagulating bath under the drive of a silk roller to obtain a semi-finished product of the hydrogel fiber;
4) And (3) post-treatment, namely freezing and thawing the semi-finished hydrogel fiber product obtained in the step (3) to obtain the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber.
In the step 3), borate ester bonds formed by the reaction of borax and hydroxyl groups of sodium alginate/polyvinyl alcohol have pH reversible response, and the reaction is carried out when the pH is high, the reaction is carried out when the pH is low, and the crosslinking is carried out when the pH is low. The pH value of the prepared sodium alginate/polyvinyl alcohol/borax spinning solution is neutral, and the borax reacts with sodium alginate and polyvinyl alcohol slowly at the moment, so that the spinning solution has good fluidity and can be spun.
Further, in the step 1), the polymerization degree of the polyvinyl alcohol particles is 1700, and the alcoholysis degree is 99 (mol%).
Further, in step 1), the concentration of the polyvinyl alcohol solution is 25wt%.
Further, in the step 1), the concentration of the sodium alginate solution is 1wt% to 6wt%.
Further, in the step 2), the mass ratio of the sodium alginate solution to the polyvinyl alcohol solution is 1:1.
Further, in the step 2), the concentration of the polyvinyl alcohol in the spinning solution is 12.5wt%.
Further, in the step 2), the borax concentration in the spinning solution is 0.25wt%.
Further, in the step 2), the concentration of sodium alginate in the spinning solution is 0.5-3 wt%.
Further, in the step 3), the coagulating bath is a sodium hydroxide solution with a mass percent concentration of 5 wt%. The coagulating bath is 5wt% sodium hydroxide, when the spinning fiber passes through the coagulating bath, borax is induced to crosslink at a high pH value to form interlocking double-crosslinked hydrogel fiber, and the concentration of the sodium hydroxide is too low, so that the spinning fiber is not well coagulated, and the hydrogel fiber is easy to break.
Further, in step 4), the freeze-thaw treatment is freezing at-20 ℃ for 24 hours, and then thawing at room temperature for 2 hours.
The beneficial effects are that:
1) The invention prepares the highly oriented polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber by wet spinning by utilizing the pH reversible response characteristic of dynamic boric acid ester bonds, realizes continuous large-scale preparation of the hydrogel fiber, and overcomes the problem of low preparation efficiency of covalent cross-linked hydrogel fiber by using a tubular mold;
2) The polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber prepared by the invention has an interlocking double-network structure, takes rigid borax crosslinked sodium alginate as a first network, takes physical crosslinked polyvinyl alcohol constructed by freezing and thawing as a second network, and further crosslinks the two networks through borax, so that the mechanical property of the hydrogel is greatly improved, and simultaneously, the negatively charged sodium alginate promotes ion transmission;
3) The invention does not involve any organic solvent in the spinning process, is more environment-friendly, and the raw materials of polyvinyl alcohol and sodium alginate used in the invention have good biocompatibility, the prepared interlocking double-network ion conductive hydrogel fiber has good biocompatibility, the conductivity of the interlocking double-network ion conductive hydrogel fiber has excellent strain response performance, and the interlocking double-network ion conductive hydrogel fiber has good application prospect in the field of flexible wearable devices (such as flexible sensors and intelligent fabrics).
Drawings
FIG. 1 is a schematic illustration of the preparation of hydrogel fibers of the interlocking dual network structure of the present invention;
FIG. 2 is a Fourier Transform Infrared (FTIR) spectrum of polyvinyl alcohol, sodium alginate, borax, sodium alginate/borax hydrogels, polyvinyl alcohol/borax hydrogel fibers and polyvinyl alcohol/borax/sodium alginate hydrogel fibers;
FIG. 3 is a graph showing the comparison of (a) mechanical properties and (b) electrical conductivity of hydrogel fibers prepared in examples 1-4 using spinning solutions with different sodium alginate contents.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
In this case, in order to avoid obscuring the present invention due to unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In the following examples, unless otherwise indicated, the raw materials or processing techniques are all those conventionally used in the art as commercially available raw materials or processing techniques.
Example 1
(1) Preparation of raw materials
Taking a certain amount of polyvinyl alcohol particles with the polymerization degree of 1700 and the alcoholysis degree of 99 (mol)% and adding deionized water, and dissolving for 2 hours at 90 ℃ to prepare a uniform and transparent solution with the concentration of 25wt% for later use;
adding sodium alginate powder into deionized water while stirring, standing for 3 hours, and continuing stirring for 2 hours after the sodium alginate is fully swelled, wherein the content of the sodium alginate is 1wt% for later use;
(2) Preparation of spinning dope
Adding sodium alginate solution into polyvinyl alcohol solution according to the mass ratio of 1:1, adding borax with required dosage while stirring, stirring for 2 hours at 90 ℃, and obtaining polyvinyl alcohol/sodium alginate/borax mixed solution after complete dissolution, wherein the borax content is 0.25wt%;
Then, centrifuging the polyvinyl alcohol/sodium alginate/borax mixed solution at a low speed, and defoaming to obtain spinning stock solution;
the concentration of polyvinyl alcohol in the spinning solution is 12.5wt%, the concentration of borax is 0.25wt% and the concentration of sodium alginate is 0.5wt%;
(3) Spinning and shaping
Extruding the obtained spinning solution through a syringe needle, and solidifying and forming the formed yarn through a coagulating bath under the drive of a yarn roller to obtain a semi-finished product of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber;
the coagulating bath is sodium hydroxide solution with the mass percentage concentration of 5 wt%;
(4) Post-treatment
And (3) further freezing the semi-finished fiber at the temperature of-20 ℃ for 24 hours, and then thawing at room temperature for 2 hours to finally obtain the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber.
The tensile strength of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber prepared in example 1 is 2.63MPa, the elongation at break is 2073%, and the conductivity is 8.02S m -1.
Example 2
(1) Preparation of raw materials
Taking a certain amount of polyvinyl alcohol particles with the polymerization degree of 1700 and the alcoholysis degree of 99 (mol)% and adding deionized water, and dissolving for 2 hours at 90 ℃ to prepare a uniform and transparent solution with the concentration of 25wt% for later use;
adding sodium alginate powder into deionized water while stirring, standing for 3 hours, and continuing stirring for 2 hours after the sodium alginate is fully swelled, wherein the content of the sodium alginate is 2wt% for later use;
(2) Preparation of spinning dope
Adding sodium alginate solution into polyvinyl alcohol solution according to the mass ratio of 1:1, adding borax with required dosage while stirring, stirring for 2 hours at 90 ℃, and obtaining polyvinyl alcohol/sodium alginate/borax mixed solution after complete dissolution, wherein the borax content is 0.25wt%;
Then, centrifuging the polyvinyl alcohol/sodium alginate/borax mixed solution at a low speed, and defoaming to obtain spinning stock solution;
The concentration of polyvinyl alcohol in the spinning solution is 12.5wt%, the concentration of borax is 0.25wt%, and the concentration of sodium alginate is 1wt%.
(3) Spinning and shaping
Extruding the obtained spinning solution through a syringe needle, and solidifying and forming the formed yarn through a coagulating bath under the drive of a yarn roller to obtain a semi-finished product of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber;
the coagulating bath is sodium hydroxide solution with the mass percentage concentration of 5 wt%;
(4) Post-treatment
And (3) further freezing the semi-finished fiber at the temperature of-20 ℃ for 24 hours, and then thawing at room temperature for 2 hours to finally obtain the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber.
The tensile strength of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber prepared in example 2 is 2.90MPa, the elongation at break is 1921%, and the conductivity is 10.51S m -1.
Example 3
(1) Preparation of raw materials
Taking a certain amount of polyvinyl alcohol particles with the polymerization degree of 1700 and the alcoholysis degree of 99 (mol)% and adding deionized water, and dissolving for 2 hours at 90 ℃ to prepare a uniform and transparent solution with the concentration of 25wt% for later use;
adding sodium alginate powder into deionized water while stirring, standing for 3 hours, and continuing stirring for 2 hours after the sodium alginate is fully swelled, wherein the content of the sodium alginate is 4wt% for later use;
(2) Preparation of spinning dope
Adding sodium alginate solution into polyvinyl alcohol solution according to the mass ratio of 1:1, adding borax with required dosage while stirring, stirring for 2 hours at 90 ℃, and obtaining polyvinyl alcohol/sodium alginate/borax mixed solution after complete dissolution, wherein the borax content is 0.25wt%;
Then, centrifuging the polyvinyl alcohol/sodium alginate/borax mixed solution at a low speed, and defoaming to obtain spinning stock solution;
the concentration of polyvinyl alcohol in the spinning solution is 12.5wt%, the concentration of borax is 0.25wt%, and the concentration of sodium alginate is 2wt%.
(3) Spinning and shaping
Extruding the obtained spinning solution through a syringe needle, and solidifying and forming the formed yarn through a coagulating bath under the drive of a yarn roller to obtain a semi-finished product of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber;
the coagulating bath is sodium hydroxide solution with the mass percentage concentration of 5 wt%;
(4) Post-treatment
And (3) further freezing the semi-finished fiber at the temperature of-20 ℃ for 24 hours, and then thawing at room temperature for 2 hours to finally obtain the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber.
The tensile strength of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber prepared in example 3 is 3.83MPa, the elongation at break is 1701%, and the conductivity is 14.67S m -1.
Example 4
(1) Preparation of raw materials
Taking a certain amount of polyvinyl alcohol particles with the polymerization degree of 1700 and the alcoholysis degree of 99 (mol)% and adding deionized water, and dissolving for 2 hours at 90 ℃ to prepare a uniform and transparent solution with the concentration of 25wt% for later use;
Adding sodium alginate powder into deionized water while stirring, standing for 3 hours, and continuing stirring for 2 hours after the sodium alginate is fully swelled, wherein the content of the sodium alginate is 6wt% for later use;
(2) Preparation of spinning dope
Adding sodium alginate solution into polyvinyl alcohol solution according to the mass ratio of 1:1, adding borax with required dosage while stirring, stirring for 2 hours at 90 ℃, and obtaining polyvinyl alcohol/sodium alginate/borax mixed solution after complete dissolution, wherein the borax content is 0.25wt%;
And then, centrifuging the polyvinyl alcohol/sodium alginate/borax mixed solution at a low speed, and defoaming to obtain a spinning solution, wherein the concentration of the polyvinyl alcohol in the spinning solution is 12.5wt%, the concentration of the borax is 0.25wt% and the concentration of the sodium alginate is 3wt%.
(3) Spinning and shaping
Extruding the obtained spinning solution through a syringe needle, and solidifying and forming the formed yarn through a coagulating bath under the drive of a yarn roller to obtain a semi-finished product of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber;
the coagulating bath is sodium hydroxide solution with the mass percentage concentration of 5 wt%;
(4) Post-treatment
And (3) further freezing the semi-finished fiber at the temperature of-20 ℃ for 24 hours, and then thawing at room temperature for 2 hours to finally obtain the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber.
The tensile strength of the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber prepared in example 4 is 4.39MPa, the elongation at break is 1488%, and the conductivity is 17.98S m -1.
As shown in fig. 1, fig. 1 is a schematic diagram of the preparation of hydrogel fibers with an interlocking dual-network structure according to the present invention, wherein (1), (2) and (3) show the evolution of the polymer crosslinked network structure at different stages in the preparation process of the hydrogel fibers, and the hydrogel fibers comprise (1) spinning solution, (2) borax crosslinked fibers, and (3) interlocking dual-network fibers. In the spinning process, the polyvinyl alcohol and sodium alginate molecules are axially oriented along the hydrogel fiber under the action of shearing force in the extrusion process by the pH value reversible response characteristic of dynamic borate bond, so as to prepare the highly oriented polyvinyl alcohol/seaweed composite hydrogel fiber. The hydrogel fiber has an interlocking double-network structure, wherein rigid Borax (Borax) crosslinked Sodium Alginate (SA) is used as a first network, physical crosslinked polyvinyl alcohol (PVA) constructed by freezing and thawing is used as a second network, the two networks are further crosslinked through Borax, the mechanical property of the hydrogel is greatly improved, and meanwhile, the negatively charged sodium alginate promotes ion transmission.
As shown in fig. 2, fig. 2 shows Fourier Transform Infrared (FTIR) spectra of polyvinyl alcohol (PVA), sodium Alginate (SA), borax (borex), sodium alginate/Borax hydrogel (BS), polyvinyl alcohol/Borax hydrogel fiber (PB), and polyvinyl alcohol/Borax/sodium alginate hydrogel fiber (PBs). It can be seen that two characteristic peaks of 1451cm -1 and 1346cm -1 are found in borax, borax/sodium alginate hydrogel, polyvinyl alcohol/borax hydrogel fiber and polyvinyl alcohol/borax/sodium alginate hydrogel fiber, which are attributed to asymmetric stretching and relaxation peaks of B-O-C, which indicate that boric acid ester bonds have been successfully introduced into the hydrogel system, and that borax, sodium alginate and polyvinyl alcohol can form covalent crosslinking structures. The above results verify that the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber forms an interlocking double-network structure crosslinked by boric acid ester bonds.
As shown in fig. 3, fig. 3 shows the mechanical properties of (a) and (b) conductivity of hydrogel fibers prepared with spinning solutions of different sodium alginate contents (0.5 wt%, 1wt%, 2wt%, 3 wt%) in example 1 (PBS 0.5), example 2 (PBS 1), example 3 (PBS 2), and example 4 (PBS 3). It is known that the tensile strength of the hydrogel fiber is gradually increased, the elongation at break is gradually decreased, and the conductivity is gradually increased with the increase of the sodium alginate content. The comparison shows that when the concentration of sodium alginate is 3wt%, the prepared polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber has optimal comprehensive electromechanical performance, the tensile strength reaches 4.31MPa, the elongation at break reaches 1487%, and the conductivity reaches 17.98S m -1.
Compared with the prior art, the specific embodiment has the following beneficial effects:
1) The invention prepares the highly oriented polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber by wet spinning by utilizing the pH reversible response characteristic of dynamic boric acid ester bonds, realizes continuous large-scale preparation of the hydrogel fiber, and overcomes the problem of low preparation efficiency of covalent cross-linked hydrogel fiber by using a tubular mold;
2) The polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber prepared by the invention has an interlocking double-network structure, takes rigid borax crosslinked sodium alginate as a first network, takes physical crosslinked polyvinyl alcohol constructed by freezing and thawing as a second network, and further crosslinks the two networks through borax, so that the mechanical property of the hydrogel is greatly improved, and simultaneously, the negatively charged sodium alginate promotes ion transmission;
3) The invention does not involve any organic solvent in the spinning process, is more environment-friendly, and the raw materials of polyvinyl alcohol and sodium alginate used in the invention have good biocompatibility, the prepared interlocking double-network ion conductive hydrogel fiber has good biocompatibility, the conductivity of the interlocking double-network ion conductive hydrogel fiber has excellent strain response performance, and the interlocking double-network ion conductive hydrogel fiber has good application prospect in the field of flexible wearable devices (such as flexible sensors and intelligent fabrics).
While the invention has been shown and described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention as defined in the following claims.
Claims (10)
1. The continuous preparation method of the high-strength and high-toughness ion conductive hydrogel fiber is characterized by comprising the following steps of:
1) The preparation of raw materials comprises the steps of taking a certain amount of polyvinyl alcohol particles, adding deionized water, dissolving for 2 hours at 90 ℃ to obtain a polyvinyl alcohol solution, adding sodium alginate powder into the deionized water while stirring, standing for 3 hours, and continuing stirring for 2 hours after the sodium alginate is fully swelled to obtain a sodium alginate solution;
2) Adding the sodium alginate solution obtained in the step 1) into the polyvinyl alcohol solution obtained in the step 1), adding a certain amount of borax while stirring, stirring at 90 ℃ for 2 hours, obtaining a mixed solution after complete dissolution, and centrifuging and defoaming the mixed solution at a low speed to obtain the spinning solution;
3) Extruding the spinning solution obtained in the step 2) through a needle head of an injector, and solidifying and forming the formed silk by a coagulating bath under the drive of a silk roller to obtain a semi-finished product of the hydrogel fiber;
4) And (3) post-treatment, namely freezing and thawing the semi-finished hydrogel fiber product obtained in the step (3) to obtain the polyvinyl alcohol/sodium alginate/borax composite hydrogel fiber.
2. The method according to claim 1, wherein in step 1), the polyvinyl alcohol particles have a degree of polymerization of 1700 and an alcoholysis degree of 99 (mol%).
3. The method according to claim 1, wherein in step 1), the concentration of the polyvinyl alcohol solution is 25wt%.
4. The method according to claim 1, wherein in step 1), the concentration of the sodium alginate solution is 1wt% to 6wt%.
5. The method according to claim 1, wherein in step 2), the mass ratio of the sodium alginate solution to the polyvinyl alcohol solution is 1:1.
6. The method according to claim 1, wherein in step 2) the concentration of polyvinyl alcohol in the spinning dope is 12.5wt%.
7. The method according to claim 1, wherein in step 2) the borax concentration in the spinning dope is 0.25wt%.
8. The method according to claim 1, wherein in step 2), the concentration of sodium alginate in the spinning dope is 0.5wt% to 3wt%.
9. The method according to claim 1, characterized in that in step 3) the coagulation bath is a sodium hydroxide solution with a concentration of 5% by weight.
10. The method according to claim 1, wherein in step 4), the freeze-thaw treatment is freezing at-20 ℃ for 24 hours and then thawing at room temperature for 2 hours.
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