CN110698697A - Preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance - Google Patents
Preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance Download PDFInfo
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Abstract
The invention discloses a preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance. The invention takes polyethyleneimine, polyvinyl alcohol and molecules containing phenylboronic acid functional groups as raw materials to prepare the polyethyleneimine-polyvinyl alcohol hydrogel. Wherein the phenylboronic acid functional group-containing molecule acts as a bridging agent, crosslinking the two hydrophilic polymers together. The amino group of polyethyleneimine can react with aldehyde group or carbonyl group containing phenylboronic acid functional group molecules to generate a dynamic reversible imine bond; the alcoholic hydroxyl group of the polyvinyl alcohol can react with a boric acid group containing a phenylboronic acid functional group molecule to generate a dynamic reversible boron ester bond; meanwhile, hydrogen bond action exists between the polyethyleneimine and polyvinyl alcohol molecules. Through the synergistic effect, the hydrogel capable of rapidly self-healing is prepared, and the hydrogel can realize excellent self-healing performance without additional stimulation.
Description
Technical Field
The invention belongs to the technical field of high molecular polymers, and particularly relates to a preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance.
Background
The self-healing hydrogel refers to a gel which can restore the initial performance and appearance after the material is damaged by external force for a certain time. Because of its reliability and durability, it is widely used in biomedical fields (tissue adhesives, controlled drug release, etc.) and electrochemical fields (soft robots, sensors, artificial skin, etc.).
Self-healing hydrogels can be classified as self-healing hydrogels and non-self-healing hydrogels according to healing conditions. The hydrogel is self-healing automatically, namely, the self-healing can be realized without additional stimulation, such as light, electricity, pH, temperature and the like. The self-healing process is simplified, the energy consumption is reduced, and the practical application of the gel is facilitated. Especially in biomedical applications, the self-healing hydrogel has great advantages because additional stimulation such as light, electricity and the like can cause damage to cells.
For the construction of self-healing hydrogels, there are two main approaches: firstly, physical crosslinking, such as construction by utilizing hydrogen bonds, ionic bonds, super-hydrophobic effect, host-guest effect and the like; the second is chemical crosslinking, which is the construction of self-healing hydrogels through dynamic covalent bonds, such as imine bonds, boroester bonds, disulfide bonds, acylhydrazone bonds, and the like.
Yixi Wang et al [ Wang Y, Niu J, Hou J, et al. A novel design structures for triple-network structures hydrogels with high-structure, tough and self-organizing properties [ J ]. Polymer, 2018, 135: 16-24 ] constructing the PAA/Agar/PVA tri-network hydrogel, wherein the gel system has the self-healing capability due to the coordination effect and the hydrogen bonding effect, and the strain self-healing efficiency reaches 84%.
Christopher C.Deng et al [ Deng C, Brooks WLA, Abboud KA, et al. Boronic acid-Based Hydrogels Undergo Self-Healing at Neutral and Acidic pH [ J ]. AcsMacro Letters, 2015, 4 (2): 220-224 takes boric acid-containing block copolymer and PVA as raw materials, and obtains hydrogel with room temperature self-healing through dynamic boron ester bond and hydrogen bond reaction crosslinking, and the hydrogel can realize complete self-healing within 60 min.
Bin Yan et al [ Yan B, Huang J, Han L, et al, duplicating Dynamic string-labeling Behavior and nanomedics of Biological Tissues in A synthetic Self-labeling Flexible Network Hydrogel [ J ]. ACS Nano, 2017: the acsnano.7b05109 ] takes aldehyde-terminated polyethylene glycol and polyethyleneimine as raw materials, and constructs the self-healing hydrogel through dynamic imine bonds and hydrogen bond action, and the hydrogel has strain hardening and excellent room-temperature self-healing capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance.
The principle of the invention is as follows:
the invention takes polyethyleneimine, polyvinyl alcohol and molecules containing phenylboronic acid functional groups as raw materials to prepare the polyethyleneimine-polyvinyl alcohol hydrogel. Wherein the phenylboronic acid functional group-containing molecule acts as a bridging agent, crosslinking the two hydrophilic polymers together. The amino group of polyethyleneimine can react with aldehyde group or carbonyl group containing phenylboronic acid functional group molecules to generate a dynamic reversible imine bond; the alcoholic hydroxyl group of the polyvinyl alcohol can react with a boric acid group containing a phenylboronic acid functional group molecule to generate a dynamic reversible boron ester bond; meanwhile, hydrogen bond action exists between the polyethyleneimine and polyvinyl alcohol molecules. Through the synergistic effect, the hydrogel capable of rapidly self-healing is prepared, and the hydrogel can realize excellent self-healing performance without additional stimulation.
The technical scheme of the invention is as follows:
a preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance is characterized by comprising the following steps: the method comprises the following steps:
(1) fully mixing and dissolving polyvinyl alcohol and a solvent at 70-98 ℃;
(2) mixing polyethyleneimine with a solvent at room temperature, and performing ultrasonic treatment until the mixture is clear;
(3) mixing a monomer containing a phenylboronic acid functional group with a solvent at room temperature, and then carrying out ultrasonic treatment until the mixture is clear;
(4) mixing the material obtained in the step (3) with the material obtained in the step (2) at room temperature, and carrying out ultrasonic treatment until the mixture is clear;
(5) dripping the material obtained in the step (4) into the material obtained in the step (1) at the temperature of 70-90 ℃ at the speed of 0.5-2 drops/s, preserving heat for reacting for 4-8 hours after dripping is finished, performing heat treatment at the temperature of 50-90 ℃ for 0-9 hours, and cooling to obtain the polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance;
the solvent is formed by mixing deionized water and an organic solvent according to the volume ratio of 1.5-2.5: 0.8-1.2, wherein the organic solvent is ethanol, methanol or DMF; the monomer containing the phenylboronic acid functional group is at least one of 4-formylphenylboronic acid, 2-formylphenylboronic acid and 4-acetylphenylboronic acid.
In a preferred embodiment of the invention, the polyvinyl alcohol is a polyvinyl alcohol 1799 type, and the alcoholysis degree is 99.8-100%.
In a preferred embodiment of the present invention, the molecular weight of the polyethyleneimine is 600-.
In a preferred embodiment of the present invention, the solvent is a mixture of deionized water and an organic solvent in a volume ratio of 2: 1
In a preferred embodiment of the invention, the mass ratio of polyethyleneimine to polyvinyl alcohol is 0.5-2: 1.
In a preferred embodiment of the present invention, the amount of the polyethyleneimine is 1.0 to 7.0 wt% based on the total amount of the polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
In a preferred embodiment of the present invention, the polyvinyl alcohol is used in an amount of 3.0 to 3.5 wt% based on the total amount of the polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional monomer and solvent.
In a preferred embodiment of the present invention, the phenylboronic acid functional group-containing monomer is used in an amount of 0 to 1.0 wt% of the total amount of the polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer, and solvent.
In a preferred embodiment of the present invention, the solvent is used in an amount of 88.5 to 96 wt% based on the total amount of the polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional monomer and solvent.
In a preferred embodiment of the present invention, the amount of the polyethyleneimine is 1.0 to 7.0 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional monomer and the solvent, the amount of the polyvinyl alcohol is 3.0 to 3.5 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional monomer and the solvent, the amount of the phenylboronic acid functional monomer is 0 to 1.0 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional monomer and the solvent, and the solvent is 88.5 to 96 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional monomer and the solvent.
The invention has the beneficial effects that:
1. the polyvinyl alcohol adopted by the invention has good biocompatibility, biodegradability and nontoxicity; the branched polyethyleneimine with low molecular weight is a high-cationic water-soluble polymer, has low toxicity, contains a large number of amino groups, is easy to crosslink, and has high drug-loading capacity as shown in the prior literature reports for many times.
2. The boron ester bond existing in the gel system is dynamic and reversible, and has responsiveness to glucose, and the phenylboronic acid group can preferentially react with the ortho-dihydroxy of the small molecular glucose, so that the gel system can be used for releasing insulin drugs;
3. the active groups (such as amino, aldehyde and the like) contained in the gel also have a drug-loading function.
4. The gel disclosed by the invention has excellent biocompatibility and biodegradability, has quick self-healing performance, and has potential application in the aspects of controlled release of drugs and the like.
5. The synthesis method has the advantages of simple process, easy operation and mild reaction conditions. The synthesized hydrogel has a rapid room-temperature self-healing function, and the strain self-healing efficiency can reach 100 percent at most within 2min
Drawings
FIG. 1 shows the reaction equation for the preparation of the polyethyleneimine-polyvinyl alcohol hydrogel according to examples 1 to 9 of the present invention.
FIG. 2 is an optical image of a polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 2 of the present invention;
FIG. 3 is an infrared spectrum of a polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 2 of the present invention.
FIG. 4 is an SEM photograph of the polyethyleneimine-polyvinyl alcohol hydrogel according to example 2, wherein a is an SEM photograph of the cross-section at 200 times and b is an SEM photograph of the cross-section at 500 times.
FIG. 5 is a stress-strain curve before and after healing of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 5 of the present invention.
FIG. 6 is a diagram illustrating the self-healing process of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
The reaction principle of the following examples is shown in FIG. 1, in which the polyvinyl alcohol is 1799 type polyvinyl alcohol and the alcoholysis degree is 99.8-100%.
Example 1:
weighing 2g of polyvinyl alcohol (PVA), dissolving in 40mL of deionized water, and dissolving for 3.5h at 90 ℃; dissolving 2g of polyethyleneimine (PEI1800) in 10mL of ethanol, and performing ultrasonic treatment for 40 min; weighing 0.15g of 4-formylphenylboronic acid, dissolving in 10mL of ethanol, and performing ultrasonic treatment for 2 min; adding 4-formylphenylboronic acid into a PEI solution at room temperature, mixing and ultrasonically treating for 30min, then dripping into a polyvinyl alcohol solution at 80 ℃, reacting for 6h to obtain a uniform viscous solution, pouring the uniform viscous solution into a beaker, carrying out heat treatment at 60 ℃ for 5h, and cooling to obtain the hydrogel PEI-PVA-1.
Table 1 examples the amounts of the components
(Note: the efficiency of the self-healing of strain is calculated from the stress-strain curve of the gel, i.e. the ratio of the maximum strain of the gel after healing for 2min to the maximum strain of the initial gel sample.)
Control group: weighing 2g of polyvinyl alcohol (PVA), dissolving in 40mL of deionized water, and dissolving for 1.5h at 95 ℃; dissolving 2g of polyethyleneimine (PEI1800) in 20mL of ethanol, and carrying out ultrasonic treatment for 30 min; and (3) dripping the polyethyleneimine solution into the polyvinyl alcohol solution at the temperature of 80 ℃, reacting for 6h to obtain a transparent solution, pouring the transparent solution into a beaker, carrying out heat treatment at the temperature of 70 ℃ for 8h, and cooling to obtain the hydrogel.
Through the control test, 4-formylphenylboronic acid can be found to promote the formation of hydrogel, which indicates that the system only depends on hydrogen bond action and can not form gel. The crosslinking between the two polymers is promoted by the generation of dynamic covalent bonds between the small molecule crosslinking agent and the polymers.
Example 2:
weighing 2g of polyvinyl alcohol (PVA), dissolving in 40mL of deionized water, and dissolving for 3.5h at 90 ℃; dissolving 2g of polyethyleneimine (PEI1800) in 10mL of ethanol, and performing ultrasonic treatment for 40 min; weighing 0.30g of 4-formylphenylboronic acid, dissolving in 10mL of ethanol, and performing ultrasonic treatment for 2 min; adding 4-formylphenylboronic acid into a PEI solution at room temperature, mixing and ultrasonically treating for 30min, dripping into a polyvinyl alcohol solution at 80 ℃, reacting for 6h to obtain a uniform viscous solution, pouring the uniform viscous solution into a beaker, carrying out heat treatment at 60 ℃ for 3h, and cooling to obtain the hydrogel PEI-PVA-2, wherein the figure is 2.
Example 3:
weighing 2g of polyvinyl alcohol (PVA), dissolving in 40mL of deionized water, and dissolving for 3.5h at 90 ℃; dissolving 2g of polyethyleneimine (PEI1800) in 10mL of ethanol, and carrying out ultrasonic treatment for 30 min; weighing 0.45g of 4-formylphenylboronic acid, dissolving in 10mL of ethanol, and performing ultrasonic treatment for 2 min; adding 4-formylphenylboronic acid into a PEI solution at room temperature, mixing and ultrasonically treating for 20min, then dripping into a polyvinyl alcohol solution at 80 ℃, reacting for 5h to obtain a uniform viscous solution, pouring the solution into a beaker, carrying out heat treatment at 60 ℃ for 1h, and cooling to obtain the hydrogel PEI-PVA-3.
Example 4:
weighing 2g of polyvinyl alcohol (PVA), dissolving in 40mL of deionized water, and dissolving for 3.5h at 90 ℃; dissolving 2g of polyethyleneimine (PEI600) in 10mL of ethanol, and performing ultrasonic treatment for 40 min; weighing 0.15g of 4-formylphenylboronic acid, dissolving in 10mL of ethanol, and performing ultrasonic treatment for 2 min; adding 4-formylphenylboronic acid into a PEI solution at room temperature, mixing and ultrasonically treating for 30min, then dripping into a polyvinyl alcohol solution at 80 ℃, reacting for 6h to obtain a uniform viscous solution, pouring the uniform viscous solution into a beaker, carrying out heat treatment at 80 ℃ for 7h, and cooling to obtain the hydrogel PEI-PVA-4.
Example 5:
weighing 2g of polyvinyl alcohol (PVA), dissolving in 40mL of deionized water, and dissolving for 3.5h at 90 ℃; dissolving 2g of polyethyleneimine (PEI10000) in 10mL of ethanol, and performing ultrasonic treatment for 60 min; weighing 0.15g of 4-formylphenylboronic acid, dissolving in 10mL of ethanol, and performing ultrasonic treatment for 2 min; adding 4-formylphenylboronic acid into a PEI solution at room temperature, mixing and ultrasonically treating for 30min, then dripping into a polyvinyl alcohol solution at 80 ℃, reacting for 6h to obtain a uniform viscous solution, pouring the uniform viscous solution into a beaker, carrying out heat treatment at 60 ℃ for 4h, and cooling to obtain the hydrogel PEI-PVA-5.
Examples 6 to 11 the same procedures as in example 1 were carried out, and the amounts of the respective components and the strain self-healing efficiencies thereof are shown in Table 1.
FIG. 3 is an infrared spectrum of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 2. The spectrum shows that: 3275cm-1Is the vibration absorption peak of-OH and- NH 2, 2918 and 2829cm-1The presence of polyethyleneimine and polyvinyl alcohol is described above as the vibration absorption peak of methylene. 1568, 1454cm-1Is a characteristic absorption peak of benzene ring skeleton, 811cm-1The introduction of the 4-formylphenylboronic acid molecule was described above for the disubstituted aryl C-H out-of-plane bending vibration peak. 1645cm-1The position is a characteristic absorption peak of a C ═ N bond, which indicates that the amino group of polyethyleneimine reacts with the aldehyde group of the 4-formylphenylboronic acid molecule; furthermore, 1371cm-1Is a characteristic peak of a B-O-C bond, and indicates the generation of a boron ester bond.
FIG. 4 is an SEM photograph of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 2. As seen from the SEM image, the prepared hydrogel is a conventional three-dimensional network-like structure (FIG. 4 a); and it has a micro-scale pore structure with a size of about 10 μm (fig. 4 b). The hydrogel system has a porous structure which is also beneficial to the loading and controlled release of the drug.
FIG. 5 is a tensile stress-strain curve before and after healing of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 5. From the graph, the black line is the stress-strain curve of the initial sample, the strength is about 60kPa, and the elongation at break can reach 1400%; the red line is the stress-strain curve of the sample after healing for 2min, which substantially coincides with the curve of the initial sample. According to corresponding calculation, the strain self-healing efficiency of the hydrogel can reach 100%, which shows that the hydrogel has excellent room-temperature self-healing capability.
Fig. 6 is a diagram illustrating a self-healing process of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in example 1. Firstly, making hydrogel into 3 small spheres, and dyeing one of the spherical gels; then, 3 spherical gels are contacted together, and after 2min, the spherical gels can be lifted by using tweezers, which shows that the hydrogel can bear the dead weight and further shows the rapid self-healing behavior.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance is characterized by comprising the following steps: the method comprises the following steps:
(1) fully mixing and dissolving polyvinyl alcohol and a solvent at 70-98 ℃;
(2) mixing polyethyleneimine with a solvent at room temperature, and performing ultrasonic treatment until the mixture is clear;
(3) mixing a monomer containing a phenylboronic acid functional group with a solvent at room temperature, and then carrying out ultrasonic treatment until the mixture is clear;
(4) mixing the material obtained in the step (3) with the material obtained in the step (2) at room temperature, and carrying out ultrasonic treatment until the mixture is clear;
(5) dripping the material obtained in the step (4) into the material obtained in the step (1) at the temperature of 70-90 ℃ at the speed of 0.5-2 drops/s, preserving heat for reacting for 4-8 hours after dripping is finished, performing heat treatment at the temperature of 50-90 ℃ for 0-9 hours, and cooling to obtain the polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance;
the solvent is formed by mixing deionized water and an organic solvent according to the volume ratio of 1.5-2.5: 0.8-1.2, wherein the organic solvent is ethanol, methanol or DMF; the monomer containing the phenylboronic acid functional group is at least one of 4-formylphenylboronic acid, 2-formylphenylboronic acid and 4-acetylphenylboronic acid.
2. The method of claim 1, wherein: the polyvinyl alcohol is 1799 type polyvinyl alcohol, and the alcoholysis degree is 99.8-100%.
3. The method of claim 1, wherein: the molecular weight of the polyethyleneimine is 600-70000.
4. The method of claim 1, wherein: the solvent is formed by mixing deionized water and an organic solvent according to the volume ratio of 2: 1.
5. The production method according to any one of claims 1 to 4, characterized in that: the mass ratio of the polyethyleneimine to the polyvinyl alcohol is 0.5-2: 1.
6. The production method according to any one of claims 1 to 4, characterized in that: the amount of the polyethyleneimine is 1.0-7.0 wt% of the total amount of the polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
7. The production method according to any one of claims 1 to 4, characterized in that: the polyvinyl alcohol is used in an amount of 3.0 to 3.5 wt% based on the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional group monomer and the solvent.
8. The production method according to any one of claims 1 to 4, characterized in that: the amount of the phenylboronic acid functional group-containing monomer is 0 to 1.0 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional group-containing monomer and the solvent.
9. The production method according to any one of claims 1 to 4, characterized in that: the solvent is used in an amount of 88.5 to 96 wt% based on the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional monomer, and solvent.
10. The production method according to any one of claims 1 to 4, characterized in that: the amount of the polyethyleneimine is 1.0-7.0 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional group monomer and the solvent, the amount of the polyvinyl alcohol is 3.0-3.5 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional group monomer and the solvent, the amount of the phenylboronic acid functional group monomer is 0-1.0 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional group monomer and the solvent, and the amount of the solvent is 88.5-96 wt% of the total amount of the polyethyleneimine, the polyvinyl alcohol, the phenylboronic acid functional group monomer and the solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910822216.9A CN110698697B (en) | 2019-08-30 | 2019-08-30 | Preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing performance |
| PCT/CN2020/112641 WO2021037269A1 (en) | 2019-08-30 | 2020-08-31 | Method for preparing polyethyleneimine-polyvinyl alcohol hydrogel having self-healing properties |
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| CN110305367A (en) * | 2019-07-23 | 2019-10-08 | 华侨大学 | A kind of ether system dynamic crosslinking agent and its application |
| CN111269443A (en) * | 2020-01-19 | 2020-06-12 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | Nano gel based on dynamic chemical bond crosslinking and preparation method and application thereof |
| CN111393675A (en) * | 2020-03-18 | 2020-07-10 | 武汉纺织大学 | Quick-forming self-healing hydrogel and preparation method thereof |
| WO2021037269A1 (en) * | 2019-08-30 | 2021-03-04 | 厦门大学 | Method for preparing polyethyleneimine-polyvinyl alcohol hydrogel having self-healing properties |
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| WO2021037269A1 (en) * | 2019-08-30 | 2021-03-04 | 厦门大学 | Method for preparing polyethyleneimine-polyvinyl alcohol hydrogel having self-healing properties |
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| CN112831065A (en) * | 2021-02-08 | 2021-05-25 | 中国科学院长春应用化学研究所 | Hydrogel dressing capable of being dissolved as required and preparation method and application thereof |
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| CN113827554B (en) * | 2021-10-22 | 2024-01-23 | 西安交通大学 | Preparation method and application of aqueous gel |
| CN114432488A (en) * | 2022-03-07 | 2022-05-06 | 中南大学 | Dual dynamic chemical bond crosslinked self-healing injectable hydrogel, and preparation method and application thereof |
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| CN114774067B (en) * | 2022-05-24 | 2023-11-21 | 深圳市哈深智材科技有限公司 | Foam type conductive gelatinous skin-friendly dressing and preparation method and application thereof |
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| CN115364895B (en) * | 2022-08-17 | 2024-03-26 | 河北科技大学 | Ionic liquid gel catalyst and preparation method and application thereof |
Also Published As
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| WO2021037269A1 (en) | 2021-03-04 |
| CN110698697B (en) | 2020-10-09 |
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