CN113736131A - Sodium alginate ionic gel and preparation method thereof - Google Patents
Sodium alginate ionic gel and preparation method thereof Download PDFInfo
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- CN113736131A CN113736131A CN202111047917.3A CN202111047917A CN113736131A CN 113736131 A CN113736131 A CN 113736131A CN 202111047917 A CN202111047917 A CN 202111047917A CN 113736131 A CN113736131 A CN 113736131A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
Abstract
The invention provides a sodium alginate ionic gel and a preparation method thereof, and relates to the technical field of hydrogel. According to the invention, a mixed solution of water and an ionic liquid is used for dissolving a methacrylic acid anhydridized sodium alginate monomer, a photoinitiator and a photocrosslinking agent, photocuring is carried out after the dissolution is finished, and the cured photocured sodium alginate ionic gel is dried to remove water, so as to obtain the sodium alginate ionic gel. The sodium alginate ionic gel prepared by the invention does not contain water, and can be stored for a long time under an open condition. In addition, the sodium alginate ionic gel prepared by the invention has higher porosity and ionic conductivity.
Description
Technical Field
The invention relates to the technical field of hydrogel, and particularly relates to sodium alginate ionic gel and a preparation method thereof.
Background
Hydrogels are a class of very hydrophilic three-dimensional network-structured gels that swell rapidly in water and in this swollen state can hold a large volume of water without dissolving. All water-soluble or hydrophilic polymers can form hydrogel through certain chemical crosslinking or physical crosslinking. These polymers can be classified into two major categories, natural and synthetic, depending on their origin. The natural hydrophilic polymer includes polysaccharides (starch, cellulose, alginic acid, hyaluronic acid, chitosan, etc.) and polypeptides (collagen, poly-L-lysine, poly-L-glutamic acid, etc.). The synthesized hydrophilic polymer comprises alcohol, acrylic acid and derivatives thereof (polyacrylic acid, polymethacrylic acid, polyacrylamide, poly-N-polyacrylamide and the like).
Sodium alginate, which is a common polysaccharide polymer, is often used as a basic material for preparing hydrogel, and the multifunction of the sodium alginate hydrogel is realized by utilizing the chelation of a sodium alginate chain segment and calcium ions. However, since most of the solvents contained in the sodium alginate hydrogel are aqueous solutions, the gel cannot be stored for a long time in an open environment due to volatilization of the aqueous solutions.
Disclosure of Invention
The sodium alginate ion gel prepared by the invention does not contain water and can be stored for a long time under open conditions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of sodium alginate ionic gel, which comprises the following steps:
mixing methacrylic acid anhydridized sodium alginate monomer, water, ionic liquid, photocrosslinking agent and photoinitiator to obtain sodium alginate photosensitive resin;
carrying out photocuring on the sodium alginate photosensitive resin to obtain photocuring sodium alginate ionic gel;
and drying the photocuring sodium alginate ionic gel to obtain the sodium alginate ionic gel.
Preferably, the ionic liquid is 1-ethyl-3-methylimidazolium acetate.
Preferably, the mass of the methacrylic anhydridized sodium alginate monomer is 2-6% of that of water; the volume of the ionic liquid accounts for 30-50% of the volume of water; the mass of the photocrosslinking agent is 10-60% of that of the methacrylic acid anhydrization sodium alginate monomer; the mass of the photoinitiator is 1-6% of that of the methacrylic acid anhydrization sodium alginate monomer.
Preferably, the mixing of the methacrylic anhydridized sodium alginate monomer, the water, the ionic liquid, the photocrosslinking agent and the photoinitiator is carried out under the condition of keeping out of the sun; the mixing temperature is room temperature, and the mixing time is 12-24 hours.
Preferably, the photo-curing of the sodium alginate photosensitive resin comprises: and 3D printing and extrusion molding are carried out on the sodium alginate photosensitive resin, and photocuring is carried out at the same time.
Preferably, the 3D printing extrusion molding conditions include: the thickness of the printing layer is 0.09-0.1 mm, the printing air pressure is 0.03-0.04 MPa, the volume of the injector of the printer is 5mL, and the printing speed is 2-10 mm/s.
Preferably, the light curing is performed by using an ultraviolet lamp; the ultraviolet wavelength of the ultraviolet lamp is 360-420 nm; the power of the ultraviolet lamp is 50-100W/cm2。
Preferably, the drying temperature is 30-60 ℃; the drying time is 3-5 days.
The invention provides the sodium alginate ionic gel prepared by the preparation method in the technical scheme.
Preferably, the ionic conductivity of the sodium alginate ionic gel is higher than 0.02S/cm.
The invention provides a preparation method of sodium alginate ionic gel, which is characterized in that a mixed solution of water and ionic liquid is used for dissolving methacrylic anhydridized sodium alginate monomers, a photoinitiator and a photocrosslinking agent, photocuring is carried out after the dissolution is finished, and the cured photocured sodium alginate ionic gel is dried to remove water, so that the sodium alginate ionic gel is obtained. The sodium alginate ionic gel prepared by the invention does not contain water, and can be stored for a long time under an open condition. In addition, the sodium alginate ionic gel prepared by the invention has higher porosity and ionic conductivity.
Drawings
FIG. 1 is a rheological property curve (shear thinning) of the sodium alginate photosensitive resin prepared in example 1;
FIG. 2 is a rheological property curve (thixotropy) of the sodium alginate photosensitive resin prepared in example 1;
fig. 3 is an image of the 3D printed sodium alginate ionic gel of example 1 under uv light;
fig. 4 is a photograph of the sodium alginate ionic gel prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of sodium alginate ionic gel, which comprises the following steps:
mixing methacrylic acid anhydridized sodium alginate monomer, water, ionic liquid, photocrosslinking agent and photoinitiator to obtain sodium alginate photosensitive resin;
carrying out photocuring on the sodium alginate photosensitive resin to obtain photocuring sodium alginate ionic gel;
and drying the photocuring sodium alginate ionic gel to obtain the sodium alginate ionic gel.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The sodium alginate photosensitive resin is obtained by mixing methacrylic acid anhydridized sodium alginate monomer, water, ionic liquid, photo-crosslinking agent and photoinitiator. In the present invention, the preparation method of the methacrylic anhydrified sodium alginate monomer preferably comprises: mixing the sodium alginate solution and methacrylic anhydride to carry out acylation reaction to obtain the methacrylic anhydridized sodium alginate monomer.
In the invention, the concentration of the sodium alginate solution is preferably 0.02 g/mL; the solvent of the sodium alginate solution is preferably water. In the present invention, the mass ratio of sodium alginate to methacrylic anhydride in the sodium alginate solution is preferably 1: (5-20), more preferably 1: (10-15).
In the present invention, the mixing process of the sodium alginate solution and methacrylic anhydride preferably comprises: and dropwise adding methacrylic anhydride into the sodium alginate solution. The rate of the dropwise addition is not particularly limited in the present invention, and may be carried out at a rate well known to those skilled in the art. In the present invention, the pH value in the dropping process is preferably controlled to 7.5 to 8.5, and more preferably controlled to 8.0. In the present invention, the pH is preferably adjusted by NaOH solution; the concentration of the NaOH solution is preferably 5 mol/L. The pH is preferably measured by pH paper.
In the invention, the acylation reaction is preferably carried out in an ice bath, and the time of the acylation reaction is preferably 24-28 h, and more preferably 24-26 h. In the present invention, it is preferable to maintain the pH of the reaction solution obtained by the mixing at 7.5 to 8.5, and it is more preferable to maintain the pH of the reaction solution obtained by the mixing at 8.0, during the acylation reaction. In the present invention, the pH is preferably adjusted by NaOH solution; the concentration of the NaOH solution is preferably 5 mol/L. The pH is preferably measured by pH paper.
After the acylation reaction is finished, the invention preferably mixes a product system obtained by the acylation reaction with the glacial ethanol, and after precipitates are separated out, the suction filtration and the drying are sequentially carried out. The invention has no special limit on the dosage of the glacial ethanol, and can ensure that the obtained methacrylic acid anhydrization sodium alginate monomer is completely separated out. The suction filtration is not particularly limited in the present invention, and may be carried out by a process known to those skilled in the art. After the suction filtration is finished, the invention also preferably comprises the step of continuing the suction filtration after the solid substance obtained by the suction filtration is subjected to ultrasonic treatment in the glacial ethanol for 1 hour to obtain white precipitate. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 30 ℃, and the time is preferably 48 hours.
After the methacrylic acid anhydridized sodium alginate monomer is obtained, the methacrylic acid anhydridized sodium alginate monomer, water, ionic liquid, a photo-crosslinking agent and a photoinitiator are mixed to obtain the sodium alginate photosensitive resin. In the present invention, the water is preferably deionized water; the ionic liquid is preferably 1-ethyl-3-methylimidazolium acetate. In the present invention, the photocrosslinker preferably comprises dimethylaminoethyl methacrylate, polyethylene glycol dimethacrylate or hydroxyethyl methacrylate; the photoinitiator preferably comprises 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone.
In the invention, the mass of the methacrylic anhydrified sodium alginate monomer is preferably 2-6% of that of water; the volume of the ionic liquid is preferably 30-50% of the volume of water, and more preferably 35-40%; the mass of the photocrosslinking agent is preferably 10-60% of that of the methacrylic acid anhydrization sodium alginate monomer, and more preferably 20-40%; the mass of the photoinitiator is preferably 1-6%, more preferably 2-4% of that of the methacrylic anhydridized sodium alginate monomer.
In the invention, the mixing of the methacrylic anhydridized sodium alginate monomer, the water, the ionic liquid, the photocrosslinking agent and the photoinitiator is preferably carried out under the condition of keeping out of the sun; the mixing temperature is preferably room temperature, and the mixing time is preferably 12-24 h.
After the sodium alginate photosensitive resin is obtained, the sodium alginate photosensitive resin is subjected to photocuring to obtain the photocuring sodium alginate ionic gel. In the present invention, the photo-curing of the sodium alginate photosensitive resin preferably comprises: and 3D printing and extrusion molding are carried out on the sodium alginate photosensitive resin, and photocuring is carried out at the same time. In the present invention, the 3D printing extrusion molding method preferably includes: and (2) filling the sodium alginate photosensitive resin into an injector of a 3D printer, extruding the sodium alginate photosensitive resin by using air, extruding the sodium alginate photosensitive resin on a glass substrate, and simultaneously carrying out photocuring in the extrusion process.
In the present invention, the 3D printing extrusion molding conditions include: the thickness of the printing layer is preferably 0.09-0.1 mm, the printing pressure is preferably 0.03-0.04 MPa, the volume of the injector of the printer is preferably 5mL, and the printing speed is preferably 2-10 mm/s, and more preferably 3-8 mm/s.
In the invention, the light curing is preferably performed by using an ultraviolet lamp; the ultraviolet wavelength of the ultraviolet lamp is preferably 360-420 nm; the power of the ultraviolet lamp is preferably 50-100W/cm2More preferably 60 to 80W/cm2. During the photocuring, a photopolymerization reaction occurs.
After the photo-curing sodium alginate ionic gel is obtained, the photo-curing sodium alginate ionic gel is dried to obtain the sodium alginate ionic gel. In the invention, the drying temperature is preferably 30-60 ℃, and more preferably 40-50 ℃; the drying time is preferably 3 to 5 days. In the present invention, the drying is preferably performed in a vacuum environment. In the drying process, water in the photocuring sodium alginate ion gel is removed, so that the sodium alginate ion gel can be stored for a long time; and meanwhile, the porosity of the sodium alginate ionic gel can be improved.
According to the invention, the aqueous solvent for dissolving methacrylic anhydridized sodium alginate monomers is replaced by the ionic liquid with similar polarity, so that the sodium alginate ionic gel with ionic conductivity is obtained, and the ionic gel can be printed and formed by a direct-writing 3D printer and has higher ionic conductivity.
The invention also provides the sodium alginate ionic gel prepared by the preparation method in the technical scheme. In the invention, the ionic conductivity of the sodium alginate ionic gel is preferably higher than 0.02S/cm, and more preferably 0.021-0.024S/cm. The sodium alginate ionic gel prepared by the method has good ionic conductivity and electric stimulation responsiveness, and can be used for aspects such as a micro sensor.
The technical solutions of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dropwise adding 0.40mol of methacrylic anhydride into 100mL of sodium alginate solution with the concentration of 0.02g/mL, measuring the pH value of the whole polymer solution by using a pH test paper in the dropwise adding process, dropwise adding a NaOH solution with the concentration of 5mol/L to keep the pH value of the whole solution at 8, and carrying out acylation reaction for 24 hours in an ice bath; and after the reaction is finished, precipitating the white reaction product in glacial ethanol, performing suction filtration, performing ultrasonic treatment on the obtained white powder in the glacial ethanol for 1h, continuing suction filtration, and performing vacuum drying on the white precipitate at the temperature of 30 ℃ for 48h to obtain the methacrylic anhydrized sodium alginate monomer.
Dissolving 0.05g of methacrylic anhydridized sodium alginate monomer in 2.45mL of deionized water and 1.35g of 1-ethyl-3-methylimidazole acetate ionic liquid, and stirring and mixing to obtain a uniform solution; then, 30mg of dimethylaminoethyl methacrylate and 3. mu.L of 2-hydroxy-2-methyl-1-phenyl-1-acetone are added and stirred overnight to obtain the sodium alginate photosensitive resin.
Pouring the sodium alginate photosensitive resin into a 5mL 3D printer injector, extruding the sodium alginate photosensitive resin by using air, extruding the sodium alginate photosensitive resin on a glass substrate, wherein the printing air pressure is 0.03MPa, the printing speed is 3mm/s, and the printing layer thickness is 2 mm; simultaneously curing by adopting an ultraviolet lamp in the extrusion process to obtain the photocuring sodium alginate ionic gel with the 3D printing square structure; the wavelength of ultraviolet light of the ultraviolet lamp is 365 nm; the power of the ultraviolet lamp is 50W/m2。
And (3) drying the photocuring sodium alginate ionic gel for 24h (time) at 30 ℃ in a vacuum environment to obtain the 3D printed sodium alginate ionic gel. An image of the sodium alginate ionic gel prepared in the example under ultraviolet light is shown in fig. 3, and the gel is a square structure with a side length of 10 cm. The shape was kept constant for 3 days under dry conditions at room temperature.
Example 2
Dropwise adding 0.40mol of methacrylic anhydride into 100mL of sodium alginate solution with the concentration of 0.02g/mL, measuring the pH value of the whole polymer solution by using a pH test paper in the dropwise adding process, dropwise adding a NaOH solution with the concentration of 5mol/L to keep the pH value of the whole solution at 8, and carrying out acylation reaction for 24 hours in an ice bath; and after the reaction is finished, precipitating the white reaction product in glacial ethanol, performing suction filtration, performing ultrasonic treatment on the obtained white powder in the glacial ethanol for 1h, continuing suction filtration, and performing vacuum drying on the white precipitate at the temperature of 30 ℃ for 48h to obtain the methacrylic anhydrized sodium alginate monomer.
Dissolving 0.2g of methacrylic anhydridized sodium alginate monomer in 2.45mL of deionized water and 1.35g of 1-ethyl-3-methylimidazole acetate ionic liquid, and stirring and mixing to obtain a uniform solution; then 20mg of dimethylaminoethyl methacrylate and 3. mu.L of 2-hydroxy-2-methyl-1-phenyl-1-propanone were added and stirred overnight to give sodium alginate photosensitive resin.
Injecting the sodium alginate photosensitive resin into a cylindrical mould at the concentration of 100mW/cm2And (3) curing for 4min under an ultraviolet point light source to obtain the photocuring sodium alginate ionic gel.
And drying the photo-curing sodium alginate ionic gel for 3 days at 40 ℃ in a vacuum environment to obtain the sodium alginate ionic gel. The ionic conductivity of the sodium alginate ionic gel prepared in the embodiment is 0.0233S/cm. The sodium alginate ionic gel is preserved for 4 days under the drying condition at room temperature, and the shape of the gel is not changed.
Example 3
Dropwise adding 0..40mol of methacrylic anhydride into 100mL of sodium alginate solution with the concentration of 0.02g/mL, measuring the pH value of the whole polymer solution by using a pH test paper in the dropwise adding process, dropwise adding a NaOH solution with the concentration of 5mol/L to keep the pH value of the whole solution at 8, and carrying out acylation reaction for 24 hours in an ice bath; and after the reaction is finished, precipitating the white reaction product in glacial ethanol, performing suction filtration, performing ultrasonic treatment on the obtained white powder in the glacial ethanol for 1h, continuing suction filtration, and performing vacuum drying on the white precipitate at the temperature of 30 ℃ for 48h to obtain the methacrylic anhydrized sodium alginate monomer.
Dissolving 0.2g of methacrylic anhydridized sodium alginate monomer in 2.45mL of deionized water and 1.35g of 1-ethyl-3-methylimidazole acetate ionic liquid, and stirring and mixing to obtain a uniform solution; then, 30mg of dimethylaminoethyl methacrylate and 3. mu.L of 2-hydroxy-2-methyl-1-phenyl-1-acetone were added, and stirred overnight to obtain the sodium alginate photosensitive resin.
Injecting the sodium alginate photosensitive resin into a cylindrical mould at the concentration of 100mW/cm2And (3) curing for 4min under an ultraviolet point light source to obtain the photocuring sodium alginate ionic gel.
And drying the photo-curing sodium alginate ionic gel for 3 days at 40 ℃ in a vacuum environment to obtain the sodium alginate ionic gel. The ionic conductivity of the sodium alginate ionic gel prepared in the embodiment is 0.02191S/cm. The sodium alginate ionic gel is preserved for 4 days under the drying condition at room temperature, and the shape of the gel is not changed.
Comparative example 1
Dropwise adding 0.40mol of methacrylic anhydride into 100mL of sodium alginate solution with the concentration of 0.02g/mL, measuring the pH value of the whole polymer solution by using a pH test paper in the dropwise adding process, dropwise adding a NaOH solution with the concentration of 5mol/L to keep the pH value of the whole solution at 8, and carrying out acylation reaction for 24 hours in an ice bath; and after the reaction is finished, precipitating the white reaction product in glacial ethanol, performing suction filtration, performing ultrasonic treatment on the obtained white powder in the glacial ethanol for 1h, continuing suction filtration, and performing vacuum drying on the white precipitate at the temperature of 30 ℃ for 48h to obtain the methacrylic anhydrized sodium alginate monomer.
Dissolving 0.2g of methacrylic anhydridized sodium alginate monomer in 2.45mL of deionized water and 2.69g of 1-ethyl-3-methylimidazole acetate ionic liquid, and stirring and mixing to obtain a uniform solution; then, 30mg of dimethylaminoethyl methacrylate and 3. mu.L of 2-hydroxy-2-methyl-1-phenyl-1-acetone were added, and stirred overnight to obtain the sodium alginate photosensitive resin.
Injecting the sodium alginate photosensitive resin into a cylindrical mould at the concentration of 100mW/cm2And (3) curing for 4min under an ultraviolet point light source to obtain the sodium alginate ionic gel which is shown in figure 4 and cannot be molded. The reason is that the ionic liquid is too much, so that the methacrylic anhydridized sodium alginate monomer has poor solubility in the solution and low crosslinking degree in the photocuring process, and cannot be molded.
Comparative example 2
Dropwise adding 0.40mol of methacrylic anhydride into 100mL of sodium alginate solution with the concentration of 0.02g/mL, measuring the pH value of the whole polymer solution by using a pH test paper in the dropwise adding process, dropwise adding a NaOH solution with the concentration of 5mol/L to keep the pH value of the whole solution at 8, and carrying out acylation reaction for 24 hours in an ice bath; and after the reaction is finished, precipitating the white reaction product in glacial ethanol, performing suction filtration, performing ultrasonic treatment on the obtained white powder in the glacial ethanol for 1h, continuing suction filtration, and performing vacuum drying on the white precipitate at the temperature of 30 ℃ for 48h to obtain the methacrylic anhydrized sodium alginate monomer.
Dissolving 0.2g of methacrylic anhydridized sodium alginate monomer in 2.45mL of deionized water, and stirring and mixing to obtain a uniform solution; then, 30mg of dimethylaminoethyl methacrylate and 3. mu.L of 2-hydroxy-2-methyl-1-phenyl-1-acetone are added and stirred overnight to obtain the sodium alginate photosensitive resin.
Injecting the sodium alginate photosensitive resin into a cylindrical mould at the concentration of 100mW/cm2And (4) curing for 4min under an ultraviolet point light source to obtain the sodium alginate hydrogel. The ionic conductivity of the sodium alginate hydrogel prepared in the comparative example is 6 multiplied by 10-4S/cm. The product is stored for 12h under dry conditions at room temperature, and the shape shrinks and curls due to water volatilization.
Comparative example 3
Dropwise adding 0.40mol of methacrylic anhydride into 100mL of sodium alginate solution with the concentration of 0.02g/mL, measuring the pH value of the whole polymer solution by using a pH test paper in the dropwise adding process, dropwise adding a NaOH solution with the concentration of 5mol/L to keep the pH value of the whole solution at 8, and carrying out acylation reaction for 24 hours in an ice bath; and after the reaction is finished, precipitating the white reaction product in glacial ethanol, performing suction filtration, performing ultrasonic treatment on the obtained white powder in the glacial ethanol for 1h, continuing suction filtration, and performing vacuum drying on the white precipitate at the temperature of 30 ℃ for 48h to obtain the methacrylic anhydrized sodium alginate monomer.
Dissolving 0.2g of methacrylic anhydridized sodium alginate monomer in 2.45mL of deionized water and 0.7g of 1-ethyl-3-methylimidazole acetate ionic liquid, and stirring and mixing to obtain a uniform solution; then, 30mg of dimethylaminoethyl methacrylate and 3. mu.L of 2-hydroxy-2-methyl-1-phenyl-1-acetone are added and stirred overnight to obtain the sodium alginate photosensitive resin. The shape was kept constant for 4 days under dry conditions at room temperature.
Injecting the sodium alginate photosensitive resin into a cylindrical mould at the concentration of 100mW/cm2And (4) curing for 4min under an ultraviolet point light source to obtain the sodium alginate hydrogel. The ionic conductivity of the sodium alginate hydrogel prepared in the comparative example is 2.156 multiplied by 10- 3S/cm. The sodium alginate ionic gel is preserved for 4 days under the drying condition at room temperature, and the shape of the gel is not changed.
Test example
Rheological property of the sodium alginate photosensitive resin prepared in the embodiment 1 of the invention is tested by using a rheological property analyzer, and the result is shown in fig. 1-2. As can be seen from fig. 1, the sodium alginate photosensitive resin has a significant shear thinning phenomenon, which is reflected in a decrease in resin viscosity with an increase in shear rate. As can be seen from FIG. 2, when the shear rate of the sodium alginate photosensitive resin is rapidly switched, the viscosity of the sodium alginate photosensitive resin is instantaneously changed, and the hysteresis effect of the sodium alginate photosensitive resin is small. As can be illustrated in FIGS. 1-2, the dropping of the ink can be controlled during the extrusion of the sodium alginate photosensitive resin, and the method is suitable for extrusion type 3D printing.
According to the invention, sodium alginate ionic gels with different structures can be prepared by combining the preparation of the sodium alginate photosensitive resin with the 3D printing technology, and the prepared sodium alginate ionic gel has higher ionic conductivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the sodium alginate ionic gel is characterized by comprising the following steps:
mixing methacrylic acid anhydridized sodium alginate monomer, water, ionic liquid, photocrosslinking agent and photoinitiator to obtain sodium alginate photosensitive resin;
carrying out photocuring on the sodium alginate photosensitive resin to obtain photocuring sodium alginate ionic gel;
and drying the photocuring sodium alginate ionic gel to obtain the sodium alginate ionic gel.
2. The method according to claim 1, wherein the ionic liquid is 1-ethyl-3-methylimidazolium acetate.
3. The preparation method according to claim 1 or 2, wherein the mass of the methacrylic anhydrified sodium alginate monomer is 2-6% of the mass of water; the volume of the ionic liquid accounts for 30-50% of the volume of water; the mass of the photocrosslinking agent is 10-60% of that of the methacrylic acid anhydrization sodium alginate monomer; the mass of the photoinitiator is 1-6% of that of the methacrylic acid anhydrization sodium alginate monomer.
4. The preparation method of claim 1, wherein the mixing of the methacrylic anhydrified sodium alginate monomer, the water, the ionic liquid, the photocrosslinking agent and the photoinitiator is carried out under the condition of keeping out light; the mixing temperature is room temperature, and the mixing time is 12-24 hours.
5. The preparation method of claim 1, wherein the photo-curing of the sodium alginate photosensitive resin comprises: and 3D printing and extrusion molding are carried out on the sodium alginate photosensitive resin, and photocuring is carried out at the same time.
6. The manufacturing method according to claim 5, wherein the conditions of the 3D printing extrusion molding include: the thickness of the printing layer is 0.09-0.1 mm, the printing air pressure is 0.03-0.04 MPa, the volume of the injector of the printer is 5mL, and the printing speed is 2-10 mm/s.
7. The production method according to claim 1 or 5, wherein the photocuring is performed using an ultraviolet lamp; the ultraviolet wavelength of the ultraviolet lamp is 360-420 nm; the power of the ultraviolet lamp is 50-100W/cm2。
8. The preparation method according to claim 1, wherein the drying temperature is 30-60 ℃; the drying time is 3-5 days.
9. The sodium alginate ionic gel prepared by the preparation method of any one of claims 1 to 8.
10. The sodium alginate ionic gel of claim 9, wherein the ionic conductivity of the sodium alginate ionic gel is higher than 0.02S/cm.
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| CN114870064A (en) * | 2022-05-09 | 2022-08-09 | 上海玮沐医疗科技有限公司 | Photo-curing composite hydrogel containing contrast agent and preparation and use methods thereof |
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| CN103788284A (en) * | 2014-01-20 | 2014-05-14 | 西安交通大学 | Preparation method for ionic liquid gel with high elongation rate and adjustable elastic modulus |
| CN112661983A (en) * | 2020-12-22 | 2021-04-16 | 中国科学院兰州化学物理研究所 | Hydrogel material for 3D printing, preparation method and application thereof, and preparation method of external stimulation dual-response sodium alginate |
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| CN103788284A (en) * | 2014-01-20 | 2014-05-14 | 西安交通大学 | Preparation method for ionic liquid gel with high elongation rate and adjustable elastic modulus |
| CN112661983A (en) * | 2020-12-22 | 2021-04-16 | 中国科学院兰州化学物理研究所 | Hydrogel material for 3D printing, preparation method and application thereof, and preparation method of external stimulation dual-response sodium alginate |
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| KAZUNARI SOEDA ETAL.,: "Outstanding features of alginate-based gel electrolyte with ionic liquid", 《JOURNAL OF POWER SOURCES》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870064A (en) * | 2022-05-09 | 2022-08-09 | 上海玮沐医疗科技有限公司 | Photo-curing composite hydrogel containing contrast agent and preparation and use methods thereof |
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