CN114437404A - Preparation method of calcium alginate porous hydrogel - Google Patents
Preparation method of calcium alginate porous hydrogel Download PDFInfo
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- CN114437404A CN114437404A CN202210193573.5A CN202210193573A CN114437404A CN 114437404 A CN114437404 A CN 114437404A CN 202210193573 A CN202210193573 A CN 202210193573A CN 114437404 A CN114437404 A CN 114437404A
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- sodium alginate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/038—Use of an inorganic compound to impregnate, bind or coat a foam, e.g. waterglass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/022—Hydrogel, i.e. a gel containing an aqueous composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of calcium alginate porous hydrogel, which comprises the following steps: a. dissolving sodium alginate in pure water to form sodium alginate water solution; b. dissolving calcium chloride in a poor organic solvent of sodium alginate to form a calcium chloride organic solution; c. freezing the sodium alginate aqueous solution obtained in the step a, and then dehydrating the frozen sodium alginate aqueous solution by using a freeze dryer to obtain porous xerogel of the sodium alginate; d. c, placing the sodium alginate porous xerogel obtained in the step c in the calcium chloride organic solution obtained in the step b, and keeping for 1-24 hours to obtain the calcium alginate porous organogel; e. and d, placing the calcium alginate porous organic gel obtained in the step d into pure water, and replacing the organic solvent in the pure water to obtain the calcium alginate porous hydrogel. The preparation method provided by the invention does not need an additional pore-forming agent or a complex pore-forming process, and can obtain a stable permanent pore structure.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of calcium alginate porous hydrogel.
Background
Sodium alginate is a byproduct after iodine and mannitol are extracted from brown algae such as kelp or gulfweed, the molecule of the sodium alginate is formed by connecting beta-D-mannuronic acid (beta-D-mannuronic acid, M) and alpha-L-guluronic acid (alpha-L-guluronic acid, G) according to a (1 → 4) bond, and the sodium alginate is a natural polysaccharide and has stability, solubility, viscosity and safety required by pharmaceutical preparation auxiliary materials. Sodium alginate has been widely used in the food industry and in the pharmaceutical field. The sodium alginate porous hydrogel is a very potential tissue engineering scaffold material. Patent CN110256856A discloses a gelatin-sodium alginate porous hydrogel, the pore-forming principle of which is free radical polymerization under freezing condition, the technique needs to chemically modify sodium alginate or gelatin, and a group capable of free radical polymerization is grafted. Patent CN106750573B discloses a chitosan-alginate porous hydrogel, the pore-forming principle of which is that a foaming agent is additionally introduced into the system, and the process control is relatively complex. Also, an alginate foam, called a porous hydrogel, is obtained by direct lyophilization of an aqueous alginate solution. However, the pore structure obtained by direct lyophilization is a thermodynamically unstable temporary pore, and when the gel is soaked in water, the pore disappears, and an alginate gel without the pore structure is obtained.
Disclosure of Invention
The invention aims to provide a preparation method of calcium alginate porous hydrogel, which does not need an additional pore-forming agent or a complex pore-forming process and can obtain a stable permanent pore structure.
Specifically, the technical scheme provided by the invention is as follows:
a preparation method of calcium alginate porous hydrogel comprises the following steps:
a. dissolving sodium alginate in pure water to form sodium alginate water solution;
b. dissolving calcium chloride in a poor organic solvent of sodium alginate to form a calcium chloride organic solution;
c. freezing the sodium alginate aqueous solution in the step a, and then dehydrating by using a freeze dryer;
d. placing the sodium alginate obtained in the step c in the calcium chloride organic solution obtained in the step b, and keeping for 1-24 hours to obtain porous calcium alginate organogel;
e. and d, placing the porous calcium alginate organogel obtained in the step d into pure water, and replacing the organic solvent in the porous calcium alginate organogel to obtain the porous calcium alginate hydrogel.
The technical idea of the invention is to obtain the sodium alginate xerogel with the temporary pore structure by freeze drying, and then convert the temporary pore structure into a stable permanent pore structure by calcium ion crosslinking. It should be noted that the water-absorbing swelling of the sodium alginate xerogel should be avoided as much as possible when the calcium ion crosslinking reaction is carried out. When the water absorption swelling speed is higher than the calcium ion crosslinking reaction speed, the size of the obtained pore structure is reduced or even disappears. Therefore, the secondary crosslinking reaction is carried out in a poor solvent for sodium alginate.
Preferably, the concentration of the sodium alginate-containing aqueous solution in the step a is 0.5-5 wt%.
Preferably, the poor solvent of sodium alginate in step b is one or more of methanol, ethanol, n-propanol, n-pentanol or ethylene glycol. The calcium chloride can be dissolved in the solvent, and the concentration of the calcium chloride is controlled to be 1-10 wt%.
Preferably, the temperature for freezing the aqueous sodium alginate solution in step c is from-196 ℃ to-5 ℃.
Preferably, the aqueous sodium alginate solution is frozen in step c using a directional freezing method.
Wherein, step c is the process of obtaining the temporary pore structure, and comprises two specific processes: firstly, the sodium alginate aqueous solution is frozen, the freezing temperature can be controlled in the process to control the size of ice crystals, and the size and the shape of the final pore structure are influenced. The higher the temperature, the larger the ice crystal size, and the larger the resulting temporary pore structure; the lower the temperature (e.g., liquid nitrogen-195 ℃), the smaller the ice crystal size, and the smaller the resulting temporary pore structure. In addition, the directional ice crystal growth can be controlled by a directional freezing technology, and a porous structure with orientation can be realized. Secondly, the ice crystals are sublimated by utilizing a freeze drying technology to obtain a temporary pore structure. The morphology of the pore structure is the repeated etching of ice crystals.
And d, fixing the temporary hole structure. Calcium ions and the carboxyl of the sodium alginate are subjected to a cross-linking reaction, so that the pore structure is fixed. The reaction condition is that the reaction is kept for 1-24 hours at normal temperature. Since the reaction medium is a poor solvent for sodium alginate, the temporary pore structure does not collapse due to swelling. If the reaction medium is replaced by a good solvent containing sodium alginate, such as water, when the swelling of the sodium alginate is dominant, the temporary pore structure is reduced or even disappears, and the hydrogel becomes a nonporous hydrogel.
Compared with the prior art, the invention has the beneficial effects that:
(1) the nature is to use the ice crystal to make the hole, without additional hole-making agent or complex hole-making process.
(2) The raw materials are natural macromolecules, no chemical synthetic substances are added, and the biological compatibility is good.
Drawings
FIG. 1 shows the porous structure of calcium alginate hydrogel in example 1 of the present invention.
FIG. 2 shows the pore structure of the calcium alginate directional porous hydrogel in example 2 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and specific embodiments, but the practical application of the invention is not limited to the embodiments shown. All other alternative embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, shall be considered to fall within the scope of protection of the present invention.
Example 1 porous hydrogel of calcium alginate
Sodium alginate (viscosity 200 +/-20 mpa.s) is dissolved in deionized water with the concentration of 5 wt%, and bubbles are removed. The sodium alginate solution is completely frozen in a refrigerator (-16 ℃) and is frozen and dried in a freeze dryer to obtain the sodium alginate porous xerogel. The calcium chloride was completely dissolved in anhydrous ethanol at a concentration of 10 wt%. And soaking the sodium alginate porous xerogel in a calcium chloride ethanol solution for 3 hours. And (3) putting the calcium alginate porous ethanol gel into a large amount of deionized water, and completely replacing ethanol to obtain the calcium alginate porous hydrogel. The laser confocal pore structure of the porous hydrogel in a hydrated state is shown in figure 1.
Example 2 oriented porous hydrogel of calcium alginate
Sodium alginate (viscosity 200 + -20 mpa.s) was dissolved in deionized water at a concentration of 10 wt% to remove air bubbles. The sodium alginate solution is directionally frozen by using liquid nitrogen (-196 ℃) and is frozen and dried in a freeze dryer to obtain the sodium alginate porous xerogel. The calcium chloride was completely dissolved in anhydrous ethanol at a concentration of 10 wt%. And soaking the sodium alginate porous xerogel in a calcium chloride ethanol solution for 3 hours. And (3) putting the calcium alginate porous ethanol gel into a large amount of deionized water, and completely replacing ethanol to obtain the calcium alginate porous hydrogel. The laser confocal pore structure of the porous gel in a hydrated state is shown in figure 2.
Claims (6)
1. The preparation method of the calcium alginate porous hydrogel is characterized by comprising the following steps:
a. dissolving sodium alginate in pure water to form sodium alginate aqueous solution;
b. dissolving calcium chloride in a poor organic solvent of sodium alginate to form a calcium chloride organic solution;
c. freezing the sodium alginate aqueous solution obtained in the step a, and then dehydrating the frozen sodium alginate aqueous solution by using a freeze dryer to obtain porous xerogel of the sodium alginate;
d. placing the sodium alginate porous xerogel obtained in the step c in the calcium chloride organic solution obtained in the step b, and keeping for 1-24 hours to obtain the calcium alginate porous organogel;
e. and d, placing the porous calcium alginate organogel obtained in the step d into pure water, and replacing the organic solvent in the porous calcium alginate organogel to obtain the porous calcium alginate hydrogel.
2. The method for preparing the porous hydrogel of calcium alginate according to claim 1, wherein the concentration of the aqueous solution of sodium alginate in step a is 0.5-10 wt%.
3. The method for preparing the porous hydrogel of calcium alginate according to claim 1, wherein the poor solvent of sodium alginate in step b is one or more of methanol, ethanol, n-propanol, n-pentanol or ethylene glycol.
4. The method for preparing the porous hydrogel of calcium alginate according to claim 1, wherein the concentration of the organic solution of calcium chloride in the step b is 1-20 wt%.
5. The method for preparing the porous hydrogel of calcium alginate according to claim 1, wherein the freezing temperature of the aqueous solution of sodium alginate in step c is-196 ℃ to-5 ℃.
6. The method for preparing the porous hydrogel of calcium alginate according to claim 1, wherein the directional freezing method is used to freeze the aqueous solution of sodium alginate in step c.
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| CN202210193573.5A CN114437404B (en) | 2022-03-01 | 2022-03-01 | Preparation method of calcium alginate porous hydrogel |
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| CN202210193573.5A CN114437404B (en) | 2022-03-01 | 2022-03-01 | Preparation method of calcium alginate porous hydrogel |
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| CN114437404B CN114437404B (en) | 2022-10-21 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877617A (en) * | 2014-02-21 | 2014-06-25 | 广西师范大学 | Injectable silk fibroin-alginate double cross-linking hydrogel and preparation method and use method thereof |
| CN105713106A (en) * | 2015-12-31 | 2016-06-29 | 华南理工大学 | Double-crosslinked sodium alginate hydrogel and preparation method and application thereof |
| CN107118385A (en) * | 2017-06-20 | 2017-09-01 | 杭州英健生物科技有限公司 | A kind of preparation method and its product of medical alginate sponge or pectin sponge |
| CN110698722A (en) * | 2019-10-10 | 2020-01-17 | 天津工业大学 | Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure |
| CN113980341A (en) * | 2021-12-20 | 2022-01-28 | 上海应用技术大学 | Preparation method of calcium alginate gel balls |
-
2022
- 2022-03-01 CN CN202210193573.5A patent/CN114437404B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877617A (en) * | 2014-02-21 | 2014-06-25 | 广西师范大学 | Injectable silk fibroin-alginate double cross-linking hydrogel and preparation method and use method thereof |
| CN105713106A (en) * | 2015-12-31 | 2016-06-29 | 华南理工大学 | Double-crosslinked sodium alginate hydrogel and preparation method and application thereof |
| CN107118385A (en) * | 2017-06-20 | 2017-09-01 | 杭州英健生物科技有限公司 | A kind of preparation method and its product of medical alginate sponge or pectin sponge |
| CN110698722A (en) * | 2019-10-10 | 2020-01-17 | 天津工业大学 | Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure |
| CN113980341A (en) * | 2021-12-20 | 2022-01-28 | 上海应用技术大学 | Preparation method of calcium alginate gel balls |
Non-Patent Citations (2)
| Title |
|---|
| L. XIE等: ""Antibiotic drug release behavior of poly (vinyl alcohol)/sodium alginate hydrogels"", 《MATERIALWISS. WERKSTOFFTECH.》 * |
| 赵飞等: "组织工程海藻酸钙多孔支架的制备和研究", 《功能材料》 * |
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