CN109382048B - Hydrogel composed of regular brick-shaped aggregates and preparation method thereof - Google Patents
Hydrogel composed of regular brick-shaped aggregates and preparation method thereof Download PDFInfo
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- CN109382048B CN109382048B CN201811375095.XA CN201811375095A CN109382048B CN 109382048 B CN109382048 B CN 109382048B CN 201811375095 A CN201811375095 A CN 201811375095A CN 109382048 B CN109382048 B CN 109382048B
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Abstract
The invention relates to hydrogel formed by regular brick-shaped aggregates and a preparation method thereof. The preparation method comprises the following steps: (1) adding a cyclic compound and a perfluorinated surfactant into a carbonate aqueous solution, and heating for reaction; (2) and (2) adding low carbon alcohol into the system reacted in the step (1), removing bubbles, and placing in a constant temperature environment until the reaction is complete to obtain the product. By controlling the types and the concentrations of the cyclic compound and the perfluorinated surfactant, the brick-shaped aggregate can realize the transformation from a nano sheet to a rhombohedral or a hexahedral aggregate, so that the aim of regulating the viscoelasticity and the microstructure of the hydrogel is fulfilled. The invention enriches the preparation field of hydrogel materials with different microstructures because the microstructure of the hydrogel has decisive influence on the performance and the application of the hydrogel, and is favorable for expanding the application of the hydrogel materials in the fields of drug transportation and controlled release systems, nano material preparation templates, supermolecule soft materials, inductors and the like.
Description
Technical Field
The invention relates to hydrogel formed by regular brick-shaped aggregates and a preparation method thereof, belonging to the field of hydrogel materials.
Background
The hydrogel refers to a three-dimensional aggregate network structure which takes water as a solvent but cannot be dissolved, and retains a large amount of water molecules after swelling so as to maintain the shape. The hydrogel material is a novel special material which is different from a solid material and a liquid material and has excellent characteristics of the solid material and the liquid material, and has wide application prospect in different fields due to the good biocompatibility and intelligent swelling characteristic of the hydrogel material.
In the middle of the twentieth century, the poly 2-hydroxyethyl methacrylate hydrogel was first applied to the biological field by Wichterle and Lim (Nature 185(1960) 117-118), and from this point on, the application of the hydrogel gradually expanded to the fields of loading and sustained release of anticancer drugs, smart materials, environmental pollution control, oilfield chemistry, and the like, and exhibited excellent characteristics and application values. Research shows that the anticancer drug loaded nano hydrogel can realize the controlled release of the anticancer drug by using thermal induction (mater.sci.eng.c 78,773(2017)) and photothermal effect (chem.commun.,52,978(2016)), and shows good anticancer performance. The light-controlled self-repairing of the supermolecule hydrogel can be realized by utilizing the photosensitive characteristic of the hydrogel in the field of intelligent materials, and the liquid seepage property of a gel film material is regulated and controlled by utilizing the photosensitive characteristic and the pressure-sensitive characteristic (adv. mater.,25,4636 (2013)). In water environment protection, organic pollutants such as humic acid and the like in sewage can be effectively removed by utilizing a submicron to micron-level three-dimensional porous network structure communicated with hydrogel, and the method has a good application prospect (Eur. Polym.J.,92,126 (2017)). In oilfield chemistry, the wormlike micelle hydrogel has good shear stability, thermal stability, sand carrying property, less filtration, good compatibility and no residue as a clean fracturing fluid for oilfields (Journal of Colloid & Interface Science 353(2011) 231-236).
The hydrogel is reported to have abundant microstructures, such as spherical vesicles, polyhedral vesicles, worm-like micelles, planar lamellar structures, and the like, and these aggregate structures are further arranged to be assembled into more complex supramolecular structures, thereby forming the supramolecular hydrogel with high viscoelasticity. Due to the polymorphic, multidimensional and multifunctional structure of the hydrogel, the hydrogel is concerned by many scholars, and the construction of hydrogels with different microstructures is a key problem in the field of hydrogel material preparation. The vesicle-structured hydrogel is used for drug encapsulation and cell membrane simulation due to the similarity with a natural biological membrane, the 3D network-structured hydrogel is used for the field of tissue engineering due to the quick self-repair and good biocompatibility, the sponge-like hydrogel is used for environmental management due to the porous structure and good swelling performance, and the worm-like micelle hydrogel is used as a clean fracturing fluid due to the good sand suspension performance. It follows that the microstructure of a hydrogel determines its applications and functions in different fields. However, hydrogels consisting of regular brick-type aggregates have only been reported so far.
Disclosure of Invention
The invention aims to provide a hydrogel and a preparation method thereof, wherein the microscopic form of the hydrogel is a regular brick-shaped aggregate, and the brick-shaped structure presents high regularity and is novel in structure.
The preparation method of the hydrogel provided by the invention comprises the following steps:
(1) adding a cyclic compound and a perfluorinated surfactant into a carbonate aqueous solution, and heating for reaction;
(2) and (2) adding low-carbon alcohol into the system reacted in the step (1), removing bubbles, and placing in a constant-temperature environment until the reaction is complete to obtain the hydrogel.
In the above preparation method, in step (1), the carbonate may be sodium carbonate or potassium carbonate;
the concentration of the carbonate aqueous solution can be 50-100 mmol.L-1Specifically, the anhydrous carbonate reference reagent which is dried to a constant amount at 270-300 ℃ can be adopted for preparation.
In the above preparation method, in step (1), the cyclic compound is cucurbituril, α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, mono (6-amino-6-deoxy) - β -cyclodextrin, carboxymethyl- β -cyclodextrin, hydroxypropyl- β -cyclodextrin, sulfobutyl- β -cyclodextrin, methyl- β -cyclodextrin or hydroxypropyl- γ -cyclodextrin;
the perfluoro surfactant is potassium perfluorohexyl sulfonate, potassium perfluorooctyl sulfonate, perfluorooctyl sulfonyl fluoride, acrylic acid (N-methyl perfluorohexyl sulfonamide) ethyl ester, polyacrylic acid 1, 1-dihydro perfluorooctyl ester or N-methyl perfluorohexyl sulfonamide ethanol.
In the above production method, in the step (1), in a system formed by the cyclic compound, the perfluoro surfactant and the aqueous sodium carbonate solution, the total concentration of the cyclic compound and the perfluoro surfactant is 50 to 200 mmol.L-1Such as 100 mmol. L-1；
The molar ratio of the cyclic compound to the perfluorinated surfactant is 1-9: 1, as 1-4: 1. 1-3: 1. 1: 1. 3: 1 or 4: 1.
in the preparation method, in the step (1), the heating temperature is 40-80 ℃, such as 60 ℃;
the reaction time is 60-180 min, such as 120 min;
the reaction was carried out with stirring.
In the above preparation method, in the step (2), the lower alcohol may be ethanol, propanol, isopropanol, n-butanol or isobutanol.
In the preparation method, in the step (2), the volume ratio of the low carbon alcohol to the carbonate aqueous solution is 2-5: 1, such as 5: 1;
adding the lower alcohol under stirring;
and (2) adding the low carbon alcohol after the system reacted in the step (1) is naturally cooled to room temperature.
In the preparation method, in the step (2), bubbles are removed by using a centrifugal mode of a centrifugal machine;
the rotating speed of the centrifugal machine for centrifugation is 500-1000 r/min
In the preparation method, in the step (2), the constant temperature environment may be a constant temperature oven, a constant temperature water bath or a constant temperature incubator with a set temperature of 25-40 ℃.
In the preparation method, in the step (2), the reaction is completely carried out for 4-8 weeks until the reaction reaches balance, and the judgment standard is that the viscoelasticity of the hydrogel is not changed when measured by a rheometer or the microstructure of the hydrogel is not changed when observed by a scanning electron microscope.
In the preparation method, in the step (2), the reaction needs to be promoted by periodically and lightly shaking with hands in the reaction process, so that the reaction is accelerated to reach the balance.
The hydrogel prepared by the method also belongs to the protection scope of the invention.
The preparation method of the hydrogel provided by the invention is simple to operate, the dosage of the reagent is small, the obtained hydrogel has higher viscoelasticity, the elastic modulus is far greater than the viscous modulus, and the hydrogel shows good mechanical properties. In addition, the hydrogel prepared by the invention is composed of closely packed brick-shaped structures, the structure is novel, and the brick-shaped structures present high regularity.
The existing surfactant hydrogel has the common structures of spherical vesicles, three-dimensional network structures, worm-shaped micelles and microtubules, and the preparation method is complex. The preparation method of the brick-shaped aggregate hydrogel provided by the invention has the advantages that the reaction conditions and the preparation process are simple and easy to control, the complex synthesis process is avoided, and the microstructure of the obtained hydrogel is a brick-shaped structure with smooth surface and high regularity. And by controlling the types and the concentrations of the cyclic compound and the perfluorinated surfactant, the brick-shaped aggregate can realize the transformation from the nano sheet to a rhombohedral shape and a hexahedron shape, so that the aim of regulating the viscoelasticity and the microstructure of the hydrogel is fulfilled. The invention enriches the preparation field of hydrogel materials with different microstructures because the microstructure of the hydrogel has decisive influence on the performance and the application of the hydrogel, and is favorable for expanding the application of the hydrogel materials in the fields of drug transportation and controlled release systems, nano material preparation templates, supermolecule soft materials, inductors and the like.
Drawings
FIG. 1 is an SEM photograph of a hydrogel prepared in example 1 of the present invention.
FIG. 2 is a viscoelastic rheological profile of the hydrogel prepared in example 1 of the present invention.
FIG. 3 is an SEM photograph of a hydrogel prepared in example 2 of the present invention.
FIG. 4 is a viscoelastic rheological profile of the hydrogel prepared in example 2 of the present invention.
FIG. 5 is an SEM photograph of a hydrogel prepared in example 3 of the present invention.
FIG. 6 is a viscoelastic rheological profile of a hydrogel prepared in example 3 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Examples 1,
Accurately weighing 10.6000g of anhydrous sodium carbonate reference reagent which is dried to a constant amount at 270-300 ℃, placing the reagent in a 300 ml beaker, adding a proper amount of distilled water for dissolving, transferring the reagent in a 1000 ml volumetric flask, diluting the reagent until the scale is uniformly shaken to obtain the anhydrous sodium carbonate reference reagent with the concentration of 100 mmol.L-1Carbon of (2)Sodium salt standard solution. 1.8837g of hydroxypropyl-beta-cyclodextrin and 0.1076g of potassium perfluorooctyl sulfonate powder are weighed and added with 10.00ml of pre-prepared sodium carbonate solution to prepare two surfactants with the total concentration of 100 mmol.L-1And the concentration ratio is 4: 1, heating and stirring the solution at the speed of 400r/min at the temperature of 60 ℃ for 120min to fully react. After the obtained solution is naturally cooled to room temperature, 2.00ml of ethanol is dripped while stirring, and after uniform mixing, the solution is placed in a centrifuge for centrifuging at the rotating speed of 1000r/min to remove entrained bubbles. And then placing the mixture in a constant-temperature oven at 25 ℃ for 4 weeks until the reaction reaches balance (the reaction is accelerated to reach balance by periodically and lightly shaking the mixture by hands, and the judgment standard is that the viscoelasticity of the hydrogel is not changed by measuring with a rheometer), so that the milky hydrogel is obtained.
The SEM picture of the hydrogel prepared in this example is shown in fig. 1, and it can be seen that the microstructure is a nano-flake, the surface is smooth and highly regular.
The viscoelastic rheological curve of the hydrogel prepared in this example is shown in fig. 2, and it can be seen that the hydrogel has high viscoelasticity, and the elastic modulus is much greater than the viscous modulus, indicating that the hydrogel has good mechanical properties.
Examples 2,
Accurately weighing 10.6000g of anhydrous potassium carbonate reference reagent which is dried to a constant amount at 270-300 ℃, placing the reagent in a 300 ml beaker, adding a proper amount of distilled water for dissolving, transferring the reagent in a 1000 ml volumetric flask, diluting the reagent until the scale is uniformly shaken to obtain the reagent with the concentration of 100 mmol.L-1Sodium carbonate standard solution. 0.4864g of alpha-cyclodextrin and 0.2285g N-methyl perfluorohexyl sulfonamide ethanol powder are weighed and added with 10.00ml of pre-prepared sodium carbonate solution to prepare two surfactants with the total concentration of 100 mmol.L-1And the concentration ratio is 1: 1, heating and stirring the solution at the speed of 400r/min at the temperature of 60 ℃ for 120min to fully react. After the obtained solution is naturally cooled to room temperature, 2.00ml of propanol is dripped while stirring, and after uniform mixing, the solution is placed in a centrifuge for centrifuging at the rotating speed of 1000r/min to remove entrained bubbles. Placing in a constant temperature oven at 25 deg.C for 4 weeks until the reaction reaches equilibrium (periodically and gently shaking with hand to promote reactionSo as to accelerate the balance; the judgment standard is that the microstructure of the hydrogel is not changed any more by observing with a scanning electron microscope), and the milky hydrogel is obtained.
The SEM picture of the hydrogel prepared in this example is shown in fig. 3, and it can be seen that the microstructure is a brick-like structure of an oblique parallelepiped, the surface is smooth and highly regular.
The viscoelastic rheological curve of the hydrogel prepared in this example is shown in fig. 4, and it can be seen that the hydrogel has high viscoelasticity, and the elastic modulus is much greater than the viscous modulus, indicating that the hydrogel has good mechanical properties.
Examples 3,
Accurately weighing 10.6000g of anhydrous sodium carbonate reference reagent which is dried to a constant amount at 270-300 ℃, placing the reagent in a 300 ml beaker, adding a proper amount of distilled water for dissolving, transferring the reagent in a 1000 ml volumetric flask, diluting the reagent until the scale is uniformly shaken to obtain the anhydrous sodium carbonate reference reagent with the concentration of 100 mmol.L-1Sodium carbonate standard solution. 0.7198g cucurbituril and 0.1255g perfluorooctyl sulfonyl fluoride powder are weighed and added with 10.00ml of pre-prepared sodium carbonate solution to prepare two surfactants with the total concentration of 100 mmol.L-1And the concentration ratio is 3: 1, heating and stirring the solution at the speed of 400r/min at the temperature of 60 ℃ for 120min to fully react. After the obtained solution is naturally cooled to room temperature, 2.00ml of propanol is dripped while stirring, and after uniform mixing, the solution is placed in a centrifuge for centrifuging at the rotating speed of 1000r/min to remove entrained bubbles. And then placing the mixture in a constant-temperature oven at 25 ℃ for 4 weeks until the reaction reaches balance (the reaction is accelerated to reach balance by periodically and lightly shaking the mixture by hands, and the judgment standard is that the viscoelasticity of the hydrogel is not changed by measuring with a rheometer), so that the milky hydrogel is obtained.
The SEM picture of the hydrogel prepared in this example is shown in fig. 5, and it can be seen that the microstructure is a brick-like structure of straight parallelepipeds, the surface is smooth and highly regular.
The viscoelastic rheological curve of the hydrogel prepared in this example is shown in fig. 6, and it can be seen that the hydrogel has high viscoelasticity, and the elastic modulus is much greater than the viscous modulus, indicating that the hydrogel has good mechanical properties.
Claims (6)
1. A method for preparing a hydrogel, comprising the steps of:
(1) adding a cyclic compound and a perfluorinated surfactant into a carbonate aqueous solution, and heating for reaction;
the carbonate is sodium carbonate or potassium carbonate;
the concentration of the carbonate aqueous solution is 50-100 mmol-1；
The cyclic compound is cucurbituril, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, mono (6-amino-6-deoxy) -beta-cyclodextrin, carboxymethyl-beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfobutyl-beta-cyclodextrin, methyl-beta-cyclodextrin or hydroxypropyl-gamma-cyclodextrin;
the perfluoro surfactant is potassium perfluorohexyl sulfonate, potassium perfluorooctyl sulfonate, perfluorooctyl sulfonyl fluoride, acrylic acid (N-methyl perfluorohexyl sulfonamide) ethyl ester, polyacrylic acid 1, 1-dihydro perfluorooctyl ester or N-methyl perfluorohexyl sulfonamide ethanol;
in a system formed by the cyclic compound, the perfluorinated surfactant and the aqueous carbonate solution, the total concentration of the cyclic compound and the perfluorinated surfactant is 50-200 mmol-1；
The molar ratio of the cyclic compound to the perfluorinated surfactant is 1-4: 1;
the heating temperature is 40-80 ℃;
the reaction time is 60-180 min;
carrying out the reaction under stirring;
(2) and (2) adding low-carbon alcohol into the system reacted in the step (1), removing bubbles, and placing in a constant-temperature environment until the reaction is complete to obtain the hydrogel, wherein the microstructure of the hydrogel is a regular brick-shaped aggregate.
2. The method of claim 1, wherein: in the step (2), the lower alcohol is ethanol, propanol, isopropanol, n-butanol or isobutanol.
3. The production method according to claim 1 or 2, characterized in that: in the step (2), the volume ratio of the low carbon alcohol to the carbonate aqueous solution is 2-5: 1;
adding the lower alcohol under stirring.
4. The production method according to claim 3, characterized in that: in the step (2), removing bubbles by using a centrifugal mode of a centrifugal machine;
the rotating speed of the centrifugal machine for centrifugation is 500-1000 r/min.
5. The method of claim 4, wherein: and (2) reacting for 4-8 weeks in a constant temperature environment at 25-40 ℃.
6. A hydrogel prepared by the method of any one of claims 1 to 5.
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