CN108409988B - Preparation method of spongy macroporous polyvinyl alcohol hydrogel - Google Patents
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Abstract
The invention discloses a preparation method of novel spongy macroporous polyvinyl alcohol hydrogel, which comprises the following steps: dissolving polyethylene glycol in a polyvinyl alcohol solution, reducing the temperature to enable the mixed solution to generate phase separation, and then adding nano hydroxyapatite into the mixed solution with the phase separation to stabilize a phase separation system. The hydrogel is formed by a circulating freezing/melting method, and polyethylene glycol and nano hydroxyapatite are washed out to obtain the polyvinyl alcohol hydrogel with a macroporous structure. Compared with the polyvinyl alcohol hydrogel prepared by a circulating freezing/melting method without adding hydroxyapatite, the hydrogel prepared by the invention has the appearance and elasticity similar to a sponge, a three-dimensional through porous structure, high porosity (the pore diameter is 30-100 mu m), and good mechanical properties and biocompatibility. The spongy macroporous polyvinyl alcohol hydrogel has great application potential in the field of biomedical materials.
Description
Technical Field
The invention relates to a preparation method of novel spongy macroporous polyvinyl alcohol hydrogel, belonging to the field of biochemical engineering.
Background
Hydrogels are hydrophilic polymers with a three-dimensional network structure produced by chemical or physical crosslinking. It can absorb a large amount of water swelling and maintain a certain shape. Typical hydrogels are often jelly-like, soft and elastic. The good water absorption, water retention and slow release characteristics show good application prospects in the fields of tissue engineering, wound dressing, drug slow release and the like.
The materials for preparing the hydrogel can be divided into two categories of natural polymer materials and chemically synthesized polymer materials, and the preparation method generally comprises physical crosslinking and chemical crosslinking, wherein the physical crosslinking refers to a network structure formed by mutually intertwining molecules through the interaction of ionic bonds, hydrogen bonds and hydrophobic bonds. Physical cross-linking is very common in nature, and plays an important role in maintaining the three-dimensional structure of biological macromolecules (such as proteins, enzymes, nucleic acids and the like) and participating in many biological reaction processes. Physical crosslinking is often dynamic, reversible, and has a significant effect on maintaining the strength and toughness of the hydrogel. Chemical crosslinking refers to a covalent crosslinking network formed by using a chemical crosslinking agent or photopolymerization, radiation polymerization and other technologies to initiate copolymerization or polycondensation reaction to generate covalent bonds. Compared with the physical crosslinking mode, the hydrogel formed by chemical crosslinking has good mechanical strength but poor toughness, and other substances can be introduced, so that the biocompatibility of the hydrogel is not as good as that of the hydrogel prepared by the physical crosslinking method.
Polyvinyl alcohol is a high molecular hydrophilic polymer, which has been widely studied and used in the biomedical field due to its good water solubility and biocompatibility. The polyvinyl alcohol solution is repeatedly frozen and thawed at low temperature and room temperature to form physical crosslinking taking hydrogen bonds as main effects, and the polyvinyl alcohol solution has excellent mechanical properties. However, the hydrogel prepared by the method generally does not have a macroporous structure, so that the application range of the hydrogel is limited.
Disclosure of Invention
The invention aims to provide a novel spongy macroporous polyvinyl alcohol hydrogel with a macroporous structure, high porosity and excellent biocompatibility and a preparation method thereof.
The invention is realized as follows:
a preparation method of spongy macroporous polyvinyl alcohol hydrogel comprises the following steps: adding polyethylene glycol into a polyvinyl alcohol solution, stirring until the polyethylene glycol is fully dissolved, standing at room temperature, adding nano hydroxyapatite when a mixed solution turns turbid from clarification, stirring to uniformly disperse the nano hydroxyapatite in the mixed solution, transferring the mixed solution into a mold, standing at room temperature, preparing hydrogel by a circulating freezing/melting method, washing with deionized water to remove the polyethylene glycol and the nano hydroxyapatite to obtain the polyvinyl alcohol hydrogel with a macroporous structure.
The preparation method of the macroporous polyvinyl alcohol hydrogel comprises the following steps:
(1) dissolving polyvinyl alcohol in deionized water at 85-98 ℃ to obtain a polyvinyl alcohol solution with the mass-volume ratio concentration of 8-12%;
(2) adding a polyethylene glycol solution with the mass volume ratio concentration of 3-10% into the polyvinyl alcohol solution obtained in the step (1), and standing at normal temperature for 0.5-1 h;
(3) when the clear mixed solution of polyvinyl alcohol and polyethylene glycol becomes turbid, dissolving nano hydroxyapatite in the mixed solution of polyvinyl alcohol and polyethylene glycol in the step (3) according to the mass-volume ratio concentration of 6-10%;
(4) standing the mixed solution obtained in the step (3) at normal temperature for 1-1.5 h; preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-18 ℃ to-20 ℃, the melting temperature is room temperature, and the circulation times are 3-7 times;
(5) and removing the polyethylene glycol and the nano-hydroxyapatite from the prepared hydrogel in deionized water to obtain the spongy macroporous polyvinyl alcohol hydrogel.
In the step (1), the molecular weight of the polyvinyl alcohol is 80,000-120,000Da, and the alcoholysis degree is more than 99%.
In the step (1), polyvinyl alcohol is dissolved in deionized water at 95 ℃.
In the step (2), the molecular weight of the polyethylene glycol is 1000-4000 Da.
In the step (3), the particle size of the nano hydroxyapatite is 10-30 nm.
The invention has the following advantages: the invention dissolves ethylene glycol in polyvinyl alcohol solution, phase separation is carried out on the mixed solution by reducing the temperature, and then nano hydroxyapatite is added into the mixed solution which is subjected to phase separation to stabilize a phase separation system. The hydrogel is formed by a circulating freezing/melting method, and polyethylene glycol and nano hydroxyapatite are washed out to obtain the polyvinyl alcohol hydrogel with a macroporous structure. Compared with the polyvinyl alcohol hydrogel prepared by a circulating freezing/melting method without adding hydroxyapatite, the hydrogel prepared by the invention has the appearance and elasticity similar to a sponge, a three-dimensional through porous structure, high porosity (the pore diameter is 30-100 mu m), and good mechanical properties and biocompatibility. The spongy macroporous polyvinyl alcohol hydrogel has good application potential in the biomedical material fields of burn and scald dressings, hemostasis and the like.
Drawings
FIG. 1 is a wet-like appearance of the polyvinyl alcohol hydrogel of example 1;
FIG. 2 is a graph of a sample of the polyvinyl alcohol hydrogel of example 1 after wet freeze-drying;
FIG. 3 is a scanning electron micrograph of a sample of the polyvinyl alcohol hydrogel of example 1;
FIG. 4 is a graph of the swelling ratio of a sample of the polyvinyl alcohol hydrogel of example 1 in deionized water;
FIG. 5 is the water retention at 25 ℃ of the polyvinyl alcohol hydrogel sample of example 1;
FIG. 6 shows the results of the CCK-8 cytotoxicity assay of the polyvinyl alcohol hydrogel sample of example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a preparation method for preparing novel spongy macroporous polyvinyl alcohol hydrogel by using polyvinyl alcohol, polyethylene glycol and nano hydroxyapatite as raw materials, which is obtained by a circulating freezing and melting process, wherein a mixed solution of the polyvinyl alcohol and the polyethylene glycol is cooled to cause phase separation, and the addition of the nano hydroxyapatite stabilizes the phase separation of the mixed solution, which is the reason for forming the macroporous hydrogel. The solution forms hydrogel with a three-dimensional structure through a circulating freezing/melting process, the nano hydroxyapatite is washed away by using deionized water, and the hydrogel with macropores and high porosity is finally obtained by using polyethylene glycol. The specific preparation method is realized by the following steps:
the method comprises the following steps: dissolving polyvinyl alcohol in deionized water at 95 ℃ to obtain a polyvinyl alcohol solution with the mass volume ratio concentration of 8-12%;
step two: dissolving polyethylene glycol in the polyvinyl alcohol solution obtained in the first step according to the mass-volume ratio concentration of 3-10%;
step three: placing the mixed solution of the polyvinyl alcohol and the polyethylene glycol in the second step at normal temperature for 0.5-1 h;
step four: dissolving nano hydroxyapatite in the mixed solution of the polyvinyl alcohol and the polyethylene glycol in the third step according to the mass-volume ratio concentration of 6-10% when the clear mixed solution of the polyvinyl alcohol and the polyethylene glycol in the third step becomes turbid;
step five: placing the mixed solution in the fourth step at normal temperature for 1-1.5 h; then preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is between 18 ℃ below zero and 20 ℃ below zero, the melting temperature is room temperature, and the circulation times are 3 to 7. And removing the polyethylene glycol and the nano-hydroxyapatite from the prepared mixed gel in deionized water to obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
In the first step, the molecular weight of the polyvinyl alcohol is 80,000-120,000Da, and the alcoholysis degree is more than 99%.
In the second step, the molecular weight of the polyethylene glycol is 1000-4000 Da.
In the fourth step, the particle size of the nano-hydroxyapatite is 20 nm.
And step five, preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-18 ℃ to-20 ℃, the melting temperature is room temperature, and the circulation times are 3-7.
Example 1
The method comprises the following steps: weighing polyvinyl alcohol with molecular weight of 89000Da, dissolving in 20ml of deionized water to obtain a polyvinyl alcohol solution with mass-volume ratio concentration of 10%, and placing in a 95 ℃ water bath kettle to stir for full dissolution;
step two: adding polyethylene glycol with the molecular weight of 1500 Da into the solution to be fully and uniformly mixed to form a uniform solution, wherein the mass-volume ratio concentration of the polyethylene glycol is 8%;
step three: placing the mixed solution of the polyvinyl alcohol and the polyethylene glycol at normal temperature for 1 h;
step four: dissolving nano hydroxyapatite into the turbid mixed solution according to the content of 10% of mass-volume ratio concentration when the mixed solution becomes turbid;
step five: standing the uniformly mixed solution at normal temperature for 1 h; and then preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-20 ℃, the melting temperature is room temperature, and the circulation times are 5 times. And removing the polyethylene glycol and the nano-hydroxyapatite from the prepared mixed gel in deionized water to obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Example 2
The method comprises the following steps: weighing polyvinyl alcohol with the molecular weight of 98000 Da, dissolving the polyvinyl alcohol in 20ml of deionized water to obtain a polyvinyl alcohol solution with the mass fraction of 10%, and placing the polyvinyl alcohol solution in a 95 ℃ water bath kettle to be stirred to be fully dissolved;
step two: adding polyethylene glycol with the molecular weight of 1500 Da into the solution to be fully and uniformly mixed to form a uniform solution, wherein the mass-volume ratio concentration of the polyethylene glycol is 8%;
step three: placing the mixed solution of the polyvinyl alcohol and the polyethylene glycol at normal temperature for 1 h;
step four: dissolving nano hydroxyapatite into the turbid mixed solution according to the content of 6% of mass-volume ratio concentration when the mixed solution becomes turbid;
step five: standing the uniformly mixed solution at normal temperature for 1 h; and then preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-20 ℃, the melting temperature is room temperature, and the circulation times are 5 times. And removing the polyethylene glycol and the nano-hydroxyapatite from the prepared mixed gel in deionized water to obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Example 3
The method comprises the following steps: weighing polyvinyl alcohol with the molecular weight of 98000 Da, dissolving the polyvinyl alcohol in 20ml of deionized water to obtain a polyvinyl alcohol solution with the mass fraction of 8%, and placing the polyvinyl alcohol solution in a 95 ℃ water bath kettle to be stirred to be fully dissolved;
step two: adding polyethylene glycol with the molecular weight of 3000 Da into the solution to be fully and uniformly mixed to form a uniform solution, wherein the mass-volume ratio concentration of the polyethylene glycol is 4%;
step three: placing the mixed solution of the polyvinyl alcohol and the polyethylene glycol at normal temperature for 1 h;
step four: dissolving nano hydroxyapatite into the turbid mixed solution according to the content of 10% of mass-volume ratio concentration when the mixed solution becomes turbid;
step five: standing the uniformly mixed solution at normal temperature for 1 h; and then preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-20 ℃, the melting temperature is room temperature, and the circulation times are 5 times. And removing the polyethylene glycol and the nano-hydroxyapatite from the prepared mixed gel in deionized water to obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Example 4
The method comprises the following steps: weighing polyvinyl alcohol with molecular weight of 89000Da, dissolving in 20ml of deionized water to obtain a polyvinyl alcohol solution with mass fraction of 8%, and placing in a 95 ℃ water bath kettle to stir for full dissolution;
step two: adding polyethylene glycol with the molecular weight of 4000 Da into the solution to be fully and uniformly mixed to form a uniform solution, wherein the mass-volume ratio concentration of the polyethylene glycol is 3%;
step three: placing the mixed solution of the polyvinyl alcohol and the polyethylene glycol at normal temperature for 1 h;
step four: dissolving nano hydroxyapatite into the turbid mixed solution according to the content of 10% of mass-volume ratio concentration when the mixed solution becomes turbid;
step five: standing the uniformly mixed solution at normal temperature for 1 h; and then preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-20 ℃, the melting temperature is room temperature, and the circulation times are 5 times. And removing the polyethylene glycol and the nano-hydroxyapatite from the prepared mixed gel in deionized water to obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Example 5
The method comprises the following steps: weighing polyvinyl alcohol with molecular weight of 89000Da, dissolving in 20ml of deionized water to obtain a polyvinyl alcohol solution with mass fraction of 10%, and placing the polyvinyl alcohol solution in a 95 ℃ water bath kettle to be stirred for full dissolution;
step two: adding polyethylene glycol with the molecular weight of 1500 Da into the solution, and fully and uniformly mixing to form a uniform solution, wherein the mass-volume ratio concentration of the polyethylene glycol is 8%.
Step three: the homogeneous solution is prepared into gel by a circulation freezing/melting method, wherein the freezing temperature is-20 ℃, the melting temperature is room temperature, and the circulation times are 5 times. And removing polyethylene glycol from the prepared mixed gel in deionized water to obtain the polyvinyl alcohol hydrogel.
In the above examples, example 5 is a comparative example, and the measurements of various performance parameters including microstructure, swelling property, water retention property and cytotoxicity were carried out on the spongy macroporous polyvinyl alcohol hydrogels prepared in the above examples 1 and 5 of the present invention, and the results are shown in FIGS. 3 to 6.
1. The hydrogel of the present invention is wet like that shown in FIG. 1, and resembles a sponge-like translucent gel.
2. The appearance of the hydrogel sample in the invention after freeze drying is shown in fig. 2, and the material is white and has a flat surface.
3. And (5) detecting the microstructure of the hydrogel.
The prepared sample was cut into pieces of about 2 μm, dried by freeze vacuum drying, and sprayed with gold on the surface. The microstructure study of the hydrogels was performed under an electron microscope.
As shown in FIG. 3, it can be seen that the hydrogel of the present invention in example 1 is porous as a result of microscopic observation, and has uniform pore size distribution and pore size of 30-100 μm, compared to example 5.
4. And (5) detecting the swelling performance of the hydrogel.
The swelling ratio of the hydrogel was measured in deionized water at 37 ℃. Weighing the hydrogel sample after freeze drying, and recording the mass as M0. Immersing in deionized water and taking out at set time point, wiping off surface water by filter paper, weighing and recording as M1。(M1-M0) Mass after water absorption of hydrogel, M0The dry weight of the hydrogel is obtained, and the ratio is the swelling ratio.
As shown in FIG. 4, compared with example 5, the hydrogel of the invention in example 1 can reach swelling equilibrium after 30min, and the swelling ratio is about 1500%; whereas the hydrogel in example 5 reached swelling equilibrium after 120min, the swelling ratio was only about 500%.
5. And (5) detecting the water retention performance of the hydrogel.
Wet hydrogel M to be brought into swelling equilibrium0Is placed in each burnThe cup was then placed in a 37 ℃ environment to measure the change in weight over time. At a predetermined time point, the hydrogel was removed and M was weighed. M and M0The specific value is the water retention rate.
As shown in fig. 5, the water retention of both hydrogels varied with time at 37 ℃, the water retention was still greater than 50% over 48h, and example 1 and example 5 were not much different from the comparative examples.
6. And (5) detecting the cytotoxicity of the hydrogel.
The test was carried out according to the test method defined in GB/T16886.5-2003 (section 5 of the evaluation of medical device biology: in vitro cytotoxicity test).
The results in FIG. 6 show that: the cytotoxicity of the material leaching liquor is tested by adopting an L929 cell CCK-8 method. After five days of culture, the cell survival rate is more than 90%, and the experimental result shows that: according to the national standard, the toxicity grade of the material is 1 grade, and the material belongs to a biomedical material which can be used with confidence.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (2)
1. A preparation method of spongy macroporous polyvinyl alcohol hydrogel is characterized by comprising the following steps: adding polyethylene glycol into a polyvinyl alcohol solution, stirring until the polyethylene glycol is fully dissolved, standing at room temperature, adding nano hydroxyapatite when a mixed solution turns turbid from clarification, fully stirring to uniformly disperse the nano hydroxyapatite in the mixed solution, transferring the mixed solution into a mold, standing at room temperature, preparing hydrogel by a circulating freezing/melting method, washing with deionized water to remove the polyethylene glycol and the nano hydroxyapatite to obtain the polyvinyl alcohol hydrogel with a macroporous structure;
the method specifically comprises the following steps:
(1) dissolving polyvinyl alcohol in deionized water at 85-98 ℃ to obtain a polyvinyl alcohol solution with the mass volume ratio concentration of 8-12%, wherein the molecular weight of the polyvinyl alcohol is 80,000-120,000Da, and the alcoholysis degree is more than 99%;
(2) adding a polyethylene glycol solution with the mass-volume ratio concentration of 3-10% into the polyvinyl alcohol solution in the step (1), and standing at normal temperature for 0.5-1 h, wherein the molecular weight of the polyethylene glycol is 1000-4000 Da;
(3) when the clear mixed solution of polyvinyl alcohol and polyethylene glycol becomes turbid, dissolving nano hydroxyapatite in the mixed solution of polyvinyl alcohol and polyethylene glycol in the step (3) according to the content of 6-10% of mass-volume ratio concentration, wherein the particle size of the nano hydroxyapatite is 10-30 nm;
(4) standing the mixed solution obtained in the step (3) at normal temperature for 1-1.5 h; preparing the gel by a circulating freezing/melting method, wherein the freezing temperature is-18 ℃ to-20 ℃, the melting temperature is room temperature, and the circulation times are 3-7 times;
(5) and removing the polyethylene glycol and the nano-hydroxyapatite from the prepared hydrogel in deionized water to obtain the spongy macroporous polyvinyl alcohol hydrogel.
2. The method of making a macroporous polyvinyl alcohol hydrogel of claim 1, wherein: in step (1), polyvinyl alcohol is dissolved in deionized water at 95 ℃.
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| CN110698719A (en) * | 2019-10-30 | 2020-01-17 | 陕西巨子生物技术有限公司 | Preparation of polyvinyl alcohol-based hydrogel |
| CN112094418B (en) * | 2020-09-27 | 2023-04-25 | 河南省科学院同位素研究所有限责任公司 | Hydrogel composite material with photothermal conversion shape memory effect and preparation method thereof |
| CN113813436B (en) * | 2021-08-18 | 2022-08-05 | 西北大学 | Preparation method of visual antibacterial anti-inflammatory dressing for treating bacterial infection type wound |
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