CN112175232A - Preparation method of conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine - Google Patents
Preparation method of conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine Download PDFInfo
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Abstract
The invention relates to the field of intelligent materials, and discloses a preparation method of a conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine, which comprises the following steps: firstly, selecting polyvinyl alcohol and polyethylene diamine as hydrogel matrixes, then uniformly dispersing a nano-cellulose-graphene conductive compound serving as a nano-reinforcing phase into the hydrogel matrixes, obtaining conductive hydrogel fibers by adopting a wet spinning method, and finally carrying out post-treatment on the synthesized hydrogel by adopting a freezing and thawing circulation method to obtain the conductive hydrogel based on the nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine. The hydrogel prepared by the invention has great application value in the fields of photoelectric devices, flexible wearable devices, sensors and the like.
Description
Technical Field
The invention relates to the field of intelligent materials, in particular to a preparation method of a conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine.
Background
Hydrogel (Hydrogel) is a gel using water as a dispersion medium, a part of hydrophobic groups and hydrophilic residues are introduced into a water-soluble polymer with a reticular cross-linked structure, the hydrophilic residues are combined with water molecules to connect the water molecules in the reticular structure, and the cross-linked polymer with the hydrophobic residues expanding in water is a polymer network system, is soft in property, can keep a certain shape and can absorb a large amount of water. The conductive hydrogel not only has high water content and biocompatibility of common hydrogel, but also has enhanced conductivity and mechanical strength due to the addition of conductive substances, and has great application value in various directions such as conductive films, coatings, sensors, biological materials, artificial muscles and the like.
Nanocellulose is a biomass material with a diameter of less than 100 nm, and is a typical polymer nanomaterial. Compared with common cellulose, the nano-cellulose has the characteristics of cellulose and nano-materials, namely large specific surface area, high crystallinity, superfine structure, good hydrophilicity, biodegradability and excellent mechanical property. The nano-cellulose raw material has wide source and abundant reserves. Based on the source of raw materials, the preparation method and the difference of fiber morphology, nanocellulose can be divided into three categories, namely cellulose nanocrystal, cellulose nanofiber, bacterial nanocellulose and the like. The composite material based on the nano-cellulose has potential application prospect in the fields of pulping and papermaking, energy storage devices, electromagnetic shielding, tissue engineering, biological medicine and the like.
The graphene is a novel carbon two-dimensional nanometer light material and has a unique single atomic layer two-dimensional crystal structure, and a large number of research results show that the graphene has the highest strength, large specific surface area, excellent electrical conductivity, thermal conductivity and other excellent properties of the known material, and the excellent properties also determine that the graphene has wide application prospects in various fields such as composite materials, electronic devices, solar energy and the like.
The hydrogel is a 'water-retaining' material formed by dispersing hydrophilic macromolecules in an aqueous phase environment, and generally has the characteristics of excellent biocompatibility, mechanical flexibility, environmental friendliness and the like. Through various physical and chemical methods, the mechanical properties of the hydrogel, such as flexibility and viscoelastic properties, can be enhanced, and the application potential of the hydrogel in the aspect of wearable sensors is further realized. Although there are many reports on gel-type mechanical sensors, a series of problems are simultaneously present. For example, in order to enhance the stretchability or strength of the gel, scientists have designed and synthesized various complex polymer materials to enhance hydrogen bonding, electrostatic attraction, metal chelation or dynamic covalent interactions in the hydrogel network by introducing special functional chemical groups into the polymer chains. The hydrogel performance is improved by molecular design just like a double-edged sword, on one hand, the mechanical property of the gel is obviously improved; however, this is accompanied by an increase in the production cost and the difficulty of synthesis, which makes the mass industrial production of gel difficult. How to make engineered hydrogel materials of desired properties in a more economical manner is a problem in the multidisciplinary field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine, and the invention changes the key link of gel performance optimization from a fussy chemical synthesis process into the regulation and control of components in gel in a mode of replacing functional group diversity by internal regulation and control, thereby greatly reducing the manufacturing cost and process.
The specific technical scheme of the invention is as follows: a preparation method of a conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine comprises the following preparation steps:
step 1): dissolving 0.016 g of 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical and 0.08-0.12 g of NaBr in 90-110 mL of deionized water, adding 0.8-1.2 g of bleached wood pulp fiber after complete dissolution, and stirring and dispersing uniformly.
Step 2): adding NaClO into the cellulose solution obtained in the step 1) for oxidation reaction, and then continuously dropwise adding NaOH solution to control the pH of the reaction system to be 9-11, so as to obtain oxidized cellulose.
TEMPO oxidation is highly selective and can convert cellulose glucose units C6The hydroxyl group on the cellulose is oxidized to a carboxyl group, and C of the cellulose glucose unit2、C3The upper hydroxyl group is not oxidized.
Step 3): filtering oxidized cellulose, washing, ultrasonically dispersing to obtain slurry, preparing into cellulose suspension, stirring in a sealed container for 6-10 days, and refrigerating for use.
The ultrasonic wave makes the nano-cellulose fully dispersed in the deionized water, and avoids the uneven distribution and agglomeration of the cellulose in the deionized water, which causes the mechanical property of the nano-cellulose to be influenced. After the cellulose is pretreated by a TEMPO oxidation method, the cellulose is treated by a mechanical method, and the nano-cellulose which is more stable in dispersion and more uniform in size and has good viscosity performance is obtained.
Step 4): and 3) adding graphene into the cellulose suspension obtained in the step 3), fully stirring uniformly, and performing ultrasonic dispersion uniformly to obtain a stable cellulose-graphene composite suspension.
Graphene with a sheet structure is extremely easy to agglomerate and overlap in a liquid phase, so that the dispersibility of the suspension is poor, and the mechanical property and the conductivity of the composite hydrogel are not ideal enough. The natural molecular structure of the nano-cellulose and the inherent water phase dispersing ability of the nano-cellulose can be used as a green dispersing agent of the graphene, so that the graphene is effectively assisted to be uniformly dispersed in the hydrogel matrix, and the graphene is carried to construct a nano-conductive network in the composite hydrogel matrix. Meanwhile, the co-addition of the nano-cellulose and the graphene can generate a coordination effect, so that the crosslinking density and the mechanical property of the composite hydrogel are further improved.
Step 5): adding polyvinyl alcohol into water, heating to 70-80 ℃, dissolving the polyvinyl alcohol by stirring, and then standing until the polyvinyl alcohol is completely dissolved.
Since polyvinyl alcohol has a certain degree of polymerization, it is necessary to promote the diffusion of solvent molecules into the polymer under a certain temperature rise and stirring condition so that polyvinyl alcohol can be swollen and dissolved.
Step 6): adding the polyethylene diamine into the polyvinyl alcohol solution obtained in the step 5) according to the mass ratio of the polyvinyl alcohol to the polyethylene diamine of (40: 60) - (30: 70), uniformly stirring, carrying out ultrasonic treatment for 10-30 minutes to form a uniform and stable mixed solution, adding the cellulose-graphene suspension obtained in the step 4) into the mixed solution, stirring for 30-50 minutes, finally adding the cross-linking agent, continuously stirring to obtain a spinning solution, and carrying out defoaming treatment on the spinning solution for later use.
The polyvinyl alcohol and the polyethylene diamine show opposite charges, and by changing the proportion of the polyvinyl alcohol and the polyethylene diamine, the maximization of the intermolecular electrostatic attraction can be realized. And the cross-linking agent is added in the reaction, so that the obtained polymer has a certain chemical bond cross-linking degree and has certain strength. The reaction time is not suitable to be too long or too short, the polymerization degree is not high when the reaction time is too short, the strength cannot meet the condition of fiber application, the reaction time cannot be too long, the polymer has too high crosslinking degree when the reaction time is too long, and the spinning solution cannot be formed for wet spinning, or the fibers are too hard and not flexible even though spinning is carried out in time, so that the fibers are hard, brittle and easy to break.
Step 7): transferring the spinning solution obtained in the step 6) into an injector, spinning by using a spinning device, solidifying the spinning solution into fibers in a coagulating bath, standing for 4-8h, taking out, and naturally drying to obtain the hydrogel fibers.
Step 8): and (2) freezing the hydrogel fiber at a temperature of between 80 ℃ below zero and 60 ℃ below zero for 3 to 5 hours, taking out, unfreezing the hydrogel fiber at room temperature for 10 to 14 hours, freezing the hydrogel fiber at a temperature of between 80 ℃ below zero and 60 ℃ below zero for 3 to 5 hours, unfreezing the hydrogel fiber, and repeating the steps for three times to form microcrystalline areas for physical crosslinking, so that the conductive hydrogel based on the nanocellulose-graphene-polyvinyl alcohol-polyethylene diamine is finally obtained.
The freezing and thawing circulation method can change the microstructure of the hydrogel, change the cluster nanoparticles into the interconnected nano-flake structure, and further enhance the mechanical property and the conductivity of the hydrogel due to the structural change.
Preferably, in step 1), the bleached wood pulp fibers are hardwood bleached kraft pulp.
Preferably, in the step 1), the molar ratio of the 2,2,6, 6-tetramethylpiperidine-1-oxyl to the NaBr is 1: 8-12.
Preferably, in the step 2), the addition amount of NaClO is 1.3-5.0 mmol per gram of cellulose.
Preferably, in the step 2), the concentration of the NaOH solution is 0.5mol/L, and the reaction time is 4-8 h.
Preferably, in step 3), the oxidized cellulose is washed 3-5 times with deionized water, the concentration of the cellulose suspension is 1.5-2.5 mg/mL, and the stirring speed is 1000-2000 rpm.
Preferably, in the step 4), the concentration of graphene in the cellulose-graphene composite suspension is 0.5-1.0 mg/mL.
Preferably, in the step 5), the Mn =89000-98000 of the polyvinyl alcohol, the alcoholysis ratio is more than 99%, and the stirring time is 1-3 h.
Preferably, in step 6), the crosslinking agent is sodium tetraborate, and the defoaming treatment is vacuuming and defoaming treatment.
Preferably, in step 7), the coagulation bath has a composition of 5wt% aqueous sodium hydroxide solution and 95wt% aqueous ethanol solution in a volume ratio of 1: 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention changes the key link of hydrogel performance optimization from a fussy chemical synthesis process into hydrogel internal component regulation and control in a mode of replacing diversity of functional groups by internal regulation and control, thereby greatly reducing the manufacturing cost and process. The polyvinyl alcohol and the polyethylene diamine are selected as the matrixes of the hydrogel, the polyvinyl alcohol and the polyethylene diamine display opposite charges, and the maximization of the intermolecular electrostatic attraction can be realized by changing the proportion of the polyvinyl alcohol and the polyethylene diamine.
(2) The nano-cellulose-graphene conductive composite serving as a nano-reinforcing phase is uniformly dispersed into a hydrogel matrix, and the nano-cellulose raw material has wide sources and abundant reserves, and has the characteristics of cellulose and nano-materials, namely large specific surface area, high crystallinity, superfine structure, good hydrophilicity, biodegradability and excellent mechanical properties. Meanwhile, the natural molecular structure of the nano-cellulose and the inherent water phase dispersing capacity of the nano-cellulose can be used as a green dispersing agent of the graphene, so that the graphene is effectively assisted to be uniformly dispersed in the hydrogel matrix, and the graphene is carried to construct a nano-conductive network in the composite hydrogel matrix. The co-addition of the nano-cellulose and the graphene can generate a coordination effect, so that the crosslinking density and the mechanical property of the composite hydrogel are further improved.
(3) The wet spinning process is adopted for spinning, the spinning technology is mature, and the large-scale production can be realized.
(4) The post-treatment of the synthesized hydrogel by adopting a freezing and thawing circulation method can change the microstructure of the hydrogel, change the cluster nanoparticles into the interconnected nano-sheet structures, and further enhance the mechanical property and the conductivity of the hydrogel due to the structural change.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Step 1): dissolving 0.016 g of TEMPO (2, 2,6, 6-tetramethyl piperidine-1-oxygen free radical) and 0.1 g of NaBr in 100 mL of deionized water, adding 1 g of bleached wood pulp fiber after complete dissolution, and vigorously stirring until the cellulose is uniformly dispersed;
step 2) adding 8 g of NaClO into the solution obtained in the step 1) for oxidation reaction, then continuously dropwise adding 0.5mol/L NaOH solution to control the pH of the reaction system to be about 10, and reacting for 6 hours;
step 3): filtering oxidized cellulose, washing with deionized water for 4 times, performing ultrasonic dispersion to obtain slurry, preparing into 2.0 mg/mL cellulose suspension, magnetically stirring in a sealed bottle for 8 days at a stirring speed of 1500 rpm, and refrigerating in a refrigerator (below 4 deg.C) for storage;
step 4): taking 100 mL of the cellulose suspension obtained in the step 3), adding 0.07 g of graphene, fully and uniformly stirring, and uniformly dispersing a polymer by virtue of ultrasonic treatment to obtain a stable cellulose-graphene compound suspension;
step 5): adding 4 g of polyvinyl alcohol (Mn =89000-98000 of the polyvinyl alcohol, and the alcoholysis rate > 99%) into 50 mL of deionized water, heating the mixture in a water bath to 75 ℃, dissolving the polyvinyl alcohol by vigorous stirring, and then standing until the polyvinyl alcohol is completely dissolved;
step 6): adding 6 g of polyethylene diamine into the polyvinyl alcohol solution obtained in the step 5), uniformly stirring, performing ultrasonic treatment for 20 minutes to form a uniform and stable solution, adding the cellulose-graphene suspension prepared in the step 4) into the mixed solution, stirring for 40 minutes, adding 1 g of sodium tetraborate cross-linking agent, continuously stirring to obtain a spinning solution, and performing vacuum-pumping defoaming treatment on the spinning solution for later use;
step 7): transferring the spinning solution obtained in the step 6) into an injector, spinning by using a spinning device, solidifying the spinning solution into fibers in a coagulating bath, standing for 6 hours, taking out and naturally drying to obtain hydrogel fibers, wherein the coagulating bath consists of a 5wt% sodium hydroxide aqueous solution and a 95wt% ethanol aqueous solution in a volume ratio of 1: 1.
Step 8): and (3) freezing the hydrogel fiber at-70 ℃ for 4h, taking out, unfreezing at room temperature for 12h, freezing at-70 ℃ for 4h, unfreezing, and repeating for three times to form microcrystalline region physical crosslinking, thereby finally obtaining the conductive hydrogel based on the nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine.
Example 2
Step 1): dissolving 0.016 g of TEMPO (2, 2,6, 6-tetramethyl piperidine-1-oxygen free radical) and 0.1 g of NaBr in 100 mL of deionized water, adding 1 g of bleached wood pulp fiber after complete dissolution, and vigorously stirring until the cellulose is uniformly dispersed;
step 2) adding 8 g of NaClO into the solution obtained in the step 1) for oxidation reaction, then continuously dropwise adding 0.5mol/L NaOH solution to control the pH of the reaction system to be about 10, and reacting for 6 hours;
step 3): filtering oxidized cellulose, washing with deionized water for 5 times, performing ultrasonic dispersion to obtain slurry, preparing into 2.0 mg/mL cellulose suspension, magnetically stirring in a sealed bottle for 10 days at a stirring speed of 1500 rpm, and refrigerating in a refrigerator (below 4 deg.C) for storage;
step 4): taking 100 mL of the cellulose suspension obtained in the step 3), adding 0.07 g of graphene, fully and uniformly stirring, and uniformly dispersing a polymer by virtue of ultrasonic treatment to obtain a stable cellulose-graphene compound suspension;
step 5): adding 5 g of polyvinyl alcohol (Mn =89000-98000 of the polyvinyl alcohol, and the alcoholysis rate > 99%) into 50 mL of deionized water, heating the mixture in a water bath to 70 ℃, dissolving the polyvinyl alcohol by vigorous stirring, and then standing until the polyvinyl alcohol is completely dissolved;
step 6): adding 5 g of polyethylene diamine into the polyvinyl alcohol solution obtained in the step 5), uniformly stirring, performing ultrasonic treatment for 20 minutes to form a uniform and stable solution, adding the cellulose-graphene suspension prepared in the step 4) into the mixed solution, stirring for 40 minutes, adding 1 g of sodium tetraborate cross-linking agent, continuously stirring to obtain a spinning solution, and performing vacuum-pumping defoaming treatment on the spinning solution for later use;
step 7): transferring the spinning solution obtained in the step 6) into an injector, spinning by using a spinning device, solidifying the spinning solution into fibers in a coagulating bath, standing for 8 hours, taking out and naturally drying to obtain hydrogel fibers, wherein the coagulating bath consists of a 5wt% sodium hydroxide aqueous solution and a 95wt% ethanol aqueous solution in a volume ratio of 1: 1.
Step 8): and (3) freezing the hydrogel fiber at-80 ℃ for 3h, taking out, unfreezing at room temperature for 10h, freezing at-80 ℃ for 3h, unfreezing, and repeating for three times to form microcrystalline region physical crosslinking, thereby finally obtaining the conductive hydrogel based on the nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine.
Example 3
Step 1): dissolving 0.016 g of TEMPO (2, 2,6, 6-tetramethyl piperidine-1-oxygen free radical) and 0.1 g of NaBr in 100 mL of deionized water, adding 1 g of bleached wood pulp fiber after complete dissolution, and vigorously stirring until the cellulose is uniformly dispersed;
step 2): adding 8 g of NaClO into the solution obtained in the step 1) for oxidation reaction, then continuously dropwise adding 0.5mol/L of NaOH solution to control the pH of the reaction system to be about 10, and reacting for 6 hours;
step 3): filtering oxidized cellulose, washing with deionized water for 3 times, performing ultrasonic dispersion to obtain slurry, preparing into 2.0 mg/mL cellulose suspension, magnetically stirring in a sealed bottle for 6 days at a stirring speed of 1500 rpm, and refrigerating in a refrigerator (below 4 deg.C) for storage;
step 4): taking 100 mL of the cellulose suspension obtained in the step 3), adding 0.07 g of graphene, fully and uniformly stirring, and uniformly dispersing a polymer by virtue of ultrasonic treatment to obtain a stable cellulose-graphene compound suspension;
step 5): adding 3 g of polyvinyl alcohol (Mn =89000-98000 of the polyvinyl alcohol, and the alcoholysis rate > 99%) into 50 mL of deionized water, heating the mixture in a water bath to 80 ℃, dissolving the polyvinyl alcohol by vigorous stirring, and then standing until the polyvinyl alcohol is completely dissolved;
step 6): adding 7 g of polyethylene diamine into the polyvinyl alcohol solution obtained in the step 5), uniformly stirring, performing ultrasonic treatment for 20 minutes to form a uniform and stable solution, adding the cellulose-graphene suspension prepared in the step 4) into the mixed solution, stirring for 40 minutes, adding 1 g of sodium tetraborate cross-linking agent, continuously stirring to obtain a spinning solution, and performing vacuum-pumping defoaming treatment on the spinning solution for later use;
step 7): transferring the spinning solution obtained in the step 6) into an injector, spinning by using a spinning device, solidifying the spinning solution into fibers in a coagulating bath, standing for 4 hours, taking out and naturally drying to obtain hydrogel fibers, wherein the coagulating bath consists of a 5wt% sodium hydroxide aqueous solution and a 95wt% ethanol aqueous solution in a volume ratio of 1: 1.
Step 8): and (3) freezing the hydrogel fiber at-60 ℃ for 5h, taking out, unfreezing at room temperature for 14h, freezing at-60 ℃ for 5h, unfreezing, and repeating for three times to form microcrystalline region physical crosslinking, thereby finally obtaining the conductive hydrogel based on the nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a conductive hydrogel based on nano-cellulose-graphene-polyvinyl alcohol-polyethylene diamine is characterized by comprising the following preparation steps:
step 1): dissolving 0.016 g of 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical and 0.08-0.12 g of NaBr in 90-110 mL of deionized water, adding 0.8-1.2 g of bleached wood pulp fiber after complete dissolution, and stirring and dispersing uniformly;
step 2): adding NaClO into the cellulose solution obtained in the step 1) for oxidation reaction, and then continuously dropwise adding NaOH solution to control the pH of the reaction system to be 9-11 to obtain oxidized cellulose;
step 3): filtering oxidized cellulose, washing, performing ultrasonic dispersion to prepare slurry, preparing a cellulose suspension, placing the cellulose suspension in a sealed container, stirring for 6-10 days, and then refrigerating for later use;
step 4): adding graphene into the cellulose suspension obtained in the step 3), fully stirring uniformly, and ultrasonically dispersing uniformly to obtain a stable cellulose-graphene compound suspension;
step 5): adding polyvinyl alcohol into water, heating to 70-80 ℃, dissolving the polyvinyl alcohol by stirring, and then standing until the polyvinyl alcohol is completely dissolved;
step 6): adding the polyethylene diamine into the polyvinyl alcohol solution obtained in the step 5) according to the mass ratio of the polyvinyl alcohol to the polyethylene diamine of (40: 60) - (30: 70), uniformly stirring, carrying out ultrasonic treatment for 10-30 minutes to form a uniform and stable mixed solution, adding the cellulose-graphene suspension obtained in the step 4) into the mixed solution, stirring for 30-50 minutes, finally adding a cross-linking agent, continuously stirring to obtain a spinning solution, and carrying out defoaming treatment on the spinning solution for later use;
step 7): transferring the spinning solution obtained in the step 6) into an injector, spinning by using a spinning device, solidifying the spinning solution into fibers in a coagulating bath, standing for 4-8h, taking out, and naturally drying to obtain hydrogel fibers;
step 8): and (2) freezing the hydrogel fiber at a temperature of between 80 ℃ below zero and 60 ℃ below zero for 3 to 5 hours, taking out, unfreezing the hydrogel fiber at room temperature for 10 to 14 hours, freezing the hydrogel fiber at a temperature of between 80 ℃ below zero and 60 ℃ below zero for 3 to 5 hours, unfreezing the hydrogel fiber, and repeating the steps for three times to form microcrystalline areas for physical crosslinking, so that the conductive hydrogel based on the nanocellulose-graphene-polyvinyl alcohol-polyethylene diamine is finally obtained.
2. The method of claim 1 wherein in step 1) the bleached wood pulp fiber is hardwood bleached kraft pulp.
3. The method according to claim 1, wherein in the step 1), the molar ratio of 2,2,6, 6-tetramethylpiperidine-1-oxyl to NaBr is 1:8 to 12.
4. The method according to claim 1, wherein the NaClO is added in an amount of 1.3 to 5.0 mmol per gram of the cellulose in step 2).
5. The method of claim 1, wherein the concentration of the NaOH solution in step 2) is 0.5mol/L and the reaction time is 4-8 h.
6. The method according to claim 1, wherein in step 3), the oxidized cellulose is washed 3 to 5 times with deionized water, the concentration of the cellulose suspension is 1.5 to 2.5 mg/mL, and the stirring speed is 1000-2000 rpm.
7. The method according to claim 1, wherein in the step 4), the concentration of graphene in the cellulose-graphene composite suspension is 0.5 to 1.0 mg/mL.
8. The method as claimed in claim 1, wherein in step 5), Mn =89000-98000 of the polyvinyl alcohol, the alcoholysis ratio > 99% and the stirring time is 1-3 h.
9. The method according to claim 1, wherein in step 6), the crosslinking agent is sodium tetraborate, and the defoaming treatment is vacuum degassing treatment.
10. The method according to claim 1, wherein in step 7), the coagulation bath has a composition of 5wt% aqueous sodium hydroxide solution and 95wt% aqueous ethanol solution in a volume ratio of 1: 1.
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