CN111763333A - Preparation method of self-repairing high-strength hydrogel - Google Patents
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Abstract
The invention relates to a preparation method of self-repairing high-strength hydrogel, which comprises the steps of firstly, utilizing an organic micromolecule compound containing disulfide bonds as a cross-linking agent, and constructing a three-dimensional reticular space system with a uniform internal structure under the induction of ultraviolet light. Secondly, adding metal ions to enable the metal ions and disulfide bonds to generate dynamic coordination bonds, constructing a second network system on the basis of the original structure, and finally preparing the self-repairing high-strength hydrogel. The tensile strength of the hydrogel can reach 0.5-2.5 MPa, the Young modulus can reach 37-325 KPa, and the tensile length can reach 100-2600%; and has good self-repairing, compression-resistant recovery and notch sensitivity resistance, and is hydrogel with great medical potential.
Description
Technical Field
The invention relates to a preparation method of self-repairing high-strength hydrogel, belonging to the field of biomedical high polymer materials.
Background
The hydrogel is a soft material with a three-dimensional reticular space structure, and the characteristics of high biocompatibility, high water content, similar framework to animal tissue and the like of the hydrogel are generally adopted, so that the hydrogel is widely developed in the biomedical fields of tissue engineering, drug release, novel medical dressings and the like, and the breakthrough of the existing medical materials is expected to be realized. However, the mechanical properties of the conventional hydrogel are far different from the mechanical strength required by human tissues, and the requirement of the development of modern medical materials cannot be met, so that the scientists propose the following different strategies for enhancing the mechanical properties of the hydrogel: (1) double Network (DN) hydrogels. The DN hydrogel is composed of two layers of polymer networks, generally, the first layer of network structure is connected tightly, the second layer of structure is loose, the structure can ensure that the hydrogel can effectively dissipate energy when encountering external force, and the macroscopic representation of the DN hydrogel is that the DN hydrogel has better mechanical property. However, the DN hydrogel still has the problems of long time consumption, poor shape plasticity and the like, and the double-layer structure of the DN hydrogel is generally composed of covalent bonds, and the structure is difficult to restore once being damaged. (2) A Slide-ring (SR) hydrogel. The crosslinking points of the SR hydrogel are formed by annular molecules, the annular molecules can be nested on the linear macromolecules to form an 8-shaped structure under the action of chemical connection, and when the stress is applied to the hydrogel from the outside, the annular molecules with the 8-shaped structure can slide on the linear macromolecules, so that the stress is dispersed, and the hydrogel is endowed with high strength performance. (3) Nanocomposite (NC) hydrogels. By means of doping organic/inorganic nano-particles in the hydrogel, a new energy dissipation system can be formed, and the mechanical strength of the hydrogel is further improved.
Although high-strength hydrogels exhibit many advantageous properties in many respects, their advantages are gradually diminished or even eliminated once their structures are destroyed, which affects the service life of the hydrogels, and thus the development of self-healing hydrogels is necessary. At present, most of the theoretical bases of self-repairing hydrogel are dynamic chemical theory, and the most important characteristic of the self-repairing hydrogel is dynamic formability. When dynamic chemical bonds are introduced into hydrogel seeds, the hydrogel can self-repair to the original state and performance when damaged. At present, hydrogel is self-repaired mainly through the actions of hydrogen bonds, coordination bonds, ionic bonds, imine bonds, acylhydrazone bonds and the like. (1) Hydrogen bonding. The bond energy of the hydrogen bond is weaker than that of a dynamic covalent bond and stronger than that of an ionic bond, and belongs to a reversible physical bond. However, the single hydrogen bond force is relatively weak, so multiple hydrogen bonds are often needed to achieve the self-repairing purpose. (2) A metal coordinate bond. The metal coordination bond also has dynamic reversibility, so that the hydrogel with self-repairing function can be prepared. (3) An ionic bond. Two materials with opposite charges are often present in ionic hydrogel, and the self-repairing mechanism of the ionic hydrogel mainly derives from the electrostatic attraction between the two materials with opposite charges. (4) An imine bond. Imine linkages are often used as dynamic cross-linking sites to prepare self-healing hydrogels. However, high strength and self-repairing are often two independent and difficult-to-fuse properties, which severely limits the application development potential of the hydrogel in the biomedical field. Therefore, it is necessary to develop a method for preparing a repairable high-strength hydrogel.
Disclosure of Invention
In view of the above-mentioned drawbacks or needs for improvement of the prior art, it is an object of the present invention to provide a method for preparing a repairable, high-strength hydrogel.
The method selects small organic molecules containing dynamic S-S bonds as a cross-linking agent, and initiates polymerization to construct a three-dimensional polymer network structure under the induction of ultraviolet light. In order to further increase the mechanical property of the gel, metal-sulfur coordination is introduced into the three-dimensional network structure, namely metal ions are introduced into the network structure to construct a second network, and finally the repairable high-strength hydrogel is prepared.
Different from the traditional thermal-initiated hydrogel, the cross-linking points generated in the polymerization process of the common small-molecular organic cross-linking agent show polydispersion and nonuniformity, while in the photopolymerization process, by utilizing the dynamic stability of S-S bonds under ultraviolet light, a random polymer network tends to have a three-dimensional polymer network structure with uniformly dispersed cross-linking points, and the uniform network structure can promote the gel to show uniform and effective energy dissipation behavior when the gel is subjected to external force, namely show high-strength mechanical performance. In addition, the reversible metal-sulfur coordination effect is utilized, and the metal-sulfur coordination bond is dynamically combined and broken under the action of microwaves, so that the broken hydrogel achieves the self-repairing purpose.
In order to achieve the above object, the present invention provides a method for preparing a repairable high-strength hydrogel, comprising the steps of:
step 1: preparation of hydrogels
Weighing a monomer, placing the monomer in a glass mold, adding ultrapure water, and performing ultrasonic treatment to completely dissolve the monomer; adding cross-linking agent, and performing ultrasonic treatment for 5 min; adding photoinitiator, and continuing ultrasound for 2 min. And (3) irradiating the obtained mixed solution under a high-pressure ultraviolet lamp for 20-40 min, and then terminating the reaction to prepare the primary hydrogel.
Step 2: preparation of Metal-containing hydrogels
And (3) putting the prepared primary hydrogel in a 60 ℃ oven for 10 h, taking out, soaking in a metal ion-containing solution for 12 h, and taking out to prepare the metal ion-containing hydrogel.
The invention has the beneficial effects that:
firstly, the high-strength hydrogel is formed by taking dynamic S-S bonds as an organic micromolecule cross-linking agent, and has the advantages of uniform internal structure, simplicity in operation, low cost and the like; secondly, the S-S bond can be coordinated with metal ions at the same time, a second layer of network system taking the metal coordination bond as a key chemical bond is formed on the basis of the original hydrogel structure, the mechanical property of the hydrogel is further improved by the layer structure, the tensile strength of the hydrogel can reach 0.5-2.5 MPa, the Young modulus can reach 37-325 KPa, and the tensile length can reach 100-2600%; and the metal coordination bond on the hydrogel section can be reversibly broken and combined again under the action of microwaves, so that the two sections can be reconnected, and the self-repairing performance is good. Besides the advantages, the invention also has good anti-compression recovery capability and anti-notch sensitivity capability.
Drawings
FIG. 1 is an optical photograph and a scanning electron microscope image of the hydrogel (containing silver), from which it can be seen that the hydrogel obtained by the preparation has a uniform internal cavity structure.
FIG. 2 is a drawing optical photograph of a hydrogel (containing silver). It can be seen from the figure that the hydrogel is superior in tensile properties.
Figure 3 is a compression optical photograph of a hydrogel (containing silver). It can be seen from the figure that the hydrogel can restore the original shape immediately after the external force is removed, and has good compression resistance.
FIG. 4 is a photograph of the notch sensitivity resistance of a hydrogel (containing silver). It can be seen from the figure that the notched hydrogels still have a strong ability to stretch.
FIG. 5 is a self-healing process for a hydrogel (containing silver). It can be seen from the figure that the hydrogel has good self-repairing capability.
Detailed Description
In order that the method illustrated by the present invention may be readily understood, the invention will now be further illustrated with reference to specific embodiments:
example 1:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of manganese-containing hydrogels
And (3) placing the preliminary hydrogel obtained by the preparation in a 60 ℃ oven for 10 h, taking out, soaking in a solution containing 3% of manganese sulfate for 12 h, and taking out to obtain the manganese-containing hydrogel.
The manganese-containing hydrogel prepared by the process has the tensile strength of 0.503 MPa, the Young modulus of 37.6 KPa and the tensile length of about 2300% at break.
Example 2:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of hydrogel containing iron
And (3) putting the prepared primary hydrogel in a 60 ℃ oven for 10 h, taking out, soaking in a ferric chloride solution containing 3% for 12 h, and taking out to prepare the ferric water-containing hydrogel.
The iron-containing hydrogel prepared by the process has the tensile strength of 0.735 MPa, the Young modulus of 61.7 KPa and the tensile length of 2600 percent at break.
Example 3:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of cobalt-containing hydrogels
And (3) placing the prepared primary hydrogel in a 60 ℃ oven for 10 h, taking out, soaking in a cobalt chloride solution containing 3% for 12 h, and taking out to prepare the cobalt-containing hydrogel.
The cobalt-containing hydrogel prepared by the process has the tensile strength of 0.944 MPa, the Young modulus of 93.0 KPa and the tensile length of 2600 percent at break.
Example 4:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of Nickel-containing hydrogels
And (3) placing the preliminary hydrogel obtained by the preparation in a 60 ℃ oven for 10 h, taking out, soaking in a nickel sulfate solution containing 5% for 12 h, and taking out to obtain the nickel-containing hydrogel.
The nickel-containing hydrogel prepared by the process has the tensile strength of 1.315 MPa, the Young modulus of 131.5KPa and the tensile length of 2600 percent at break.
Example 5:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of copper-containing hydrogels
And (3) placing the preliminary hydrogel obtained by the preparation in a 60 ℃ oven for 10 h, taking out, soaking in a copper sulfate solution containing 5% for 12 h, and taking out to obtain the copper-containing hydrogel.
The copper-containing hydrogel prepared by the process has the tensile strength of 1.940 MPa, the Young modulus of 204.0 KPa and the tensile length of 2500% at break.
Example 6:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of silver-containing hydrogels
And (3) placing the preliminary hydrogel obtained by the preparation in a 60 ℃ oven for 10 h, taking out, soaking in a silver nitrate solution containing 3% for 12 h, and taking out to obtain the silver-containing hydrogel.
The silver-containing hydrogel prepared by the process has the tensile strength of 2.551 MPa, the Young modulus of 325.0 KPa and the tensile length of 2300% at break.
Example 7:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of silver-containing hydrogels
And (3) placing the preliminary hydrogel obtained by the preparation in a 60 ℃ oven for 10 h, taking out, soaking in a silver nitrate solution containing 1.5% for 12 h, and taking out to obtain the silver-containing hydrogel.
The silver-containing hydrogel prepared by the process has the tensile strength of 1.873 MPa, the Young modulus of 188.0 KPa and the tensile length of about 2100 percent at break.
Example 8:
1. preparation of hydrogels
Acrylamide is added into pure water to be completely dissolved by ultrasonic treatment, N, N-bis (acryloyl) cystamine is added for ultrasonic treatment for 5 min, then 2-hydroxy-4 '- (2-hydroxyethoxy) -2-methyl propiophenone is added for ultrasonic treatment for 2 min, and 20% of acryloyl, 0.05% of N, N-bis (acryloyl) cystamine, 0.1% of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and the balance of pure water are contained in the formed mixed solution (by mass ratio). And (3) irradiating the obtained mixed solution for 30 min under a high-pressure ultraviolet lamp to prepare the hydrogel.
2. Preparation of silver-containing hydrogels
And (3) placing the preliminary hydrogel obtained by the preparation in a 60 ℃ oven for 10 h, taking out, soaking in a silver nitrate solution containing 6% for 12 h, and taking out to obtain the silver-containing hydrogel.
The silver-containing hydrogel prepared by the process has the tensile strength of 2.215 MPa, the Young modulus of 243.5 KPa and the tensile length of 2300% at break.
In conclusion, the hydrogel prepared by the invention takes organic micromolecules containing dynamic S-S bonds as a cross-linking agent, induces S-S bond recombination under ultraviolet light, and further constructs a three-dimensional reticular space system with uniform internal structure. When the space structure bears external force, energy can be effectively dissipated, and the space structure is not easy to break; and the metal-sulfur coordination bond formed based on the dynamic coordination of the metal ions and the disulfide bond can further disperse energy and further improve the mechanical properties of the hydrogel. In addition, the metal-sulfur coordination bond can be dynamically combined and broken under the microwave condition, so that the metal-sulfur between the broken surfaces of the hydrogel is generated again, the self-repairing purpose is realized, and the hydrogel has good repairing performance. In conclusion, the hydrogel prepared by the method has strong mechanical properties and self-repairing capability, and is hydrogel with great medical potential.
Claims (8)
1. A preparation method of self-repairing high-strength hydrogel comprises the steps of firstly, utilizing an organic micromolecular compound containing disulfide bonds as a cross-linking agent, and constructing a three-dimensional reticular space system with a uniform internal structure under the induction of ultraviolet light; secondly, adding metal ions to enable the metal ions and disulfide bonds to generate dynamic coordination bonds, constructing a second network system on the basis of the original structure, and finally preparing the self-repairing high-strength hydrogel.
2. The method for producing a self-repairing high-strength hydrogel as described in claim 1, wherein:
step 1: preparation of hydrogels
Weighing a monomer, placing the monomer in a glass mold, adding ultrapure water, and performing ultrasonic treatment to completely dissolve the monomer; adding cross-linking agent, and performing ultrasonic treatment for 5 min; adding photoinitiator, and continuing ultrasound for 2 min;
irradiating the obtained mixed solution under a high-pressure ultraviolet lamp for 20-40 min, and then terminating the reaction to prepare hydrogel;
step 2: preparation of Metal-containing hydrogels
And (3) putting the hydrogel obtained by the preparation into a 60 ℃ oven for 10 h, taking out, soaking in a solution containing metal ions for 12 h, and taking out to obtain the hydrogel containing metal ions.
3. The method for producing a self-repairing high-strength hydrogel as described in claim 2, wherein:
in the step 1, the monomer is acrylamide, and the addition mass of the monomer is 10-40% of the total mass.
4. The method for producing a self-repairing high-strength hydrogel as described in claim 2, wherein:
in step 1, the cross-linking agent isN, N-cysteamine (acryloyl) in an amount of 0.01 to 1% by weight of the total mass.
5. The method for producing a self-repairing high-strength hydrogel as described in claim 2, wherein:
in the step 1, the initiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and the addition mass is 0.05-3% of the total mass.
6. The method for producing a self-repairing high-strength hydrogel as described in claim 2, wherein:
in the step 1, the power of the ultraviolet lamp is 200-400W, and the distance between the die and the ultraviolet lamp is 20-40 cm.
7. The method for producing a self-repairing high-strength hydrogel as described in claim 2, wherein:
in the step 2, the metal ions are any one or any combination of more than two of manganese ions, iron ions, cobalt ions, nickel ions, copper ions and silver ions.
8. The method for producing a self-repairing high-strength hydrogel as described in claim 2, wherein:
in the step 2, the concentration of the metal ion solution is 0.01-10%.
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| CN112812263B (en) * | 2021-01-06 | 2022-10-25 | 山东师范大学 | Preparation method and application of self-healing hydrogel |
| CN113040579A (en) * | 2021-03-19 | 2021-06-29 | 北京理工大学 | Self-healing gel ice cup without melting |
| CN114773624A (en) * | 2022-03-21 | 2022-07-22 | 安徽中医药大学 | Hydrogel constructed by coordination of macromolecule self-assembly and metal coordination |
| CN115337530A (en) * | 2022-09-05 | 2022-11-15 | 安徽中医药大学 | Colchicine aqueous alkali gel microneedle and preparation method thereof |
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