CN114805859B - Preparation method of heat-setting chitosan hydrogel - Google Patents
Preparation method of heat-setting chitosan hydrogel Download PDFInfo
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- CN114805859B CN114805859B CN202210679092.5A CN202210679092A CN114805859B CN 114805859 B CN114805859 B CN 114805859B CN 202210679092 A CN202210679092 A CN 202210679092A CN 114805859 B CN114805859 B CN 114805859B
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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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
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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Abstract
The preparation method of the heat-setting chitosan hydrogel comprises the following steps: s1: chitosan with deacetylation degree more than 95% is dissolved in acetic acid solution with volume concentration of 1% or hydrochloric acid solution with molar concentration of 1% to prepare chitosan solution with concentration of (1-3) wt%; s2: adding NaOH solution into chitosan solution under stirring, and stirring uniformly, wherein the concentration of NaOH added per ml of 1.1 wt% chitosan solution is (1.25-25) x 10 ‑6 mol; s3: adding a metal nitrate solution into the system obtained in the step S2; s4: and (3) heating the system obtained in the step (S3) to more than 80 ℃ and less than 100 ℃ to obtain the heat-set chitosan hydrogel. The invention has few reports on forming gel by heating and reducing temperature to form the thermo-reversible gel of sol, and the application space of the hydrogel is further widened by forming the hydrogel under the heating state.
Description
Technical Field
The invention relates to a preparation method of hydrogel, in particular to a preparation method of heat-setting chitosan hydrogel, and belongs to the technical field of chemistry.
Background
The hydrogel is a three-dimensional network structure cross-linked substance capable of absorbing and maintaining a large amount of water, has the characteristics of good biocompatibility, stimulus responsiveness, easiness in functionalization and the like, and has wide application in the fields of biochemistry, medicine and health, agriculture, environmental protection and the like. A thermoreversible gel is a gel that can be melted and reformed depending on the temperature. Most of the thermoreversible gels are characterized by being thermoreversible by being converted from a sol to a gel as the temperature decreases and from the gel to the sol upon reheating. Hydrogels can be classified into natural hydrogels and artificial hydrogels according to the source of the gel molecules. The materials of the synthetic hydrogel can be classified into natural polymers and synthetic molecules. The artificially synthesized molecules are often obtained by petrochemical refining or organic synthesis polymerization, and the preparation process is complex, expensive and non-renewable. Therefore, development of hydrogels based on naturally renewable polymers is of great importance.
Disclosure of Invention
The present invention aims to develop a heat-set hydrogel based on natural renewable polymers.
In order to achieve the purpose of the invention, the following technical scheme is adopted: the preparation method of the heat-setting chitosan hydrogel comprises the following steps:
s1: chitosan with deacetylation degree more than 95% is dissolved in acetic acid solution with volume concentration of 1% or hydrochloric acid solution with molar concentration of 1% to prepare chitosan solution with concentration of (1-3) wt%, and viscosity of chitosan is 100-200 mpa.s;
s2: adding NaOH solution into chitosan solution under stirring, and stirring uniformly, wherein the concentration of NaOH added per ml of 1.1 wt% chitosan solution is (1.25-25) x 10 -6 mol, the concentration of NaOH solution is 0.4-0.7. 0.7M;
s3: adding a metal nitrate solution into the system obtained in the step S2, and uniformly stirring; the metal nitrate solution comprises Ni (NO 3 ) 2 、Cu(NO 3 ) 2 、Zn(NO 3 ) 2 、Cd(NO 3 ) 2 、Co(NO 3 ) 2 The concentration of the metal nitrate solution is 0.4-0.7M, and the nitrate added into the chitosan solution with the concentration of 2.0-wt percent per milliliter is (0.9-1.1) multiplied by 10 -4 mol；
S4: and (3) heating the system obtained in the step (S3) to more than 80 ℃ and less than 100 ℃ to obtain the heat-set chitosan hydrogel.
Further; and (3) cooling the heat-set chitosan hydrogel obtained in the step (S4) to normal temperature, and changing the heat-set chitosan hydrogel into sol with good fluidity.
Further; the nitrate metal salt solution is Ni (NO) 3 ) 2 The preparation method of the solution comprises the following steps: dissolving chitosan with deacetylation degree of more than 95% in acetic acid solution with volume concentration of 1% to obtain chitosan solution with concentration of 2.0 wt%, mixing 2mL solution, adding 30 μl NaOH solution with concentration of 0.5M, stirring, adding 400 μl Ni (NO) with concentration of 0.5M 3 ) 2 And (3) uniformly stirring the solution, and then heating to 95 ℃ to obtain the heat-setting chitosan hydrogel.
Further; the gel forming time of the heat-setting chitosan hydrogel is less than or equal to 3min.
Further; the heat-setting chitosan hydrogel is clear and transparent, and the circulation times are more than 100 times.
The invention has the positive and beneficial technical effects that: chitosan is an alkaline aminopolysaccharide formed from natural chitin by deacetylation, and is widely found in nature. According to the invention, natural chitosan is used as a raw material, acetic acid and hydrochloric acid are used as solvents, and after metal ions are added, the completely reversible heat-setting hydrogel is prepared by increasing the temperature of the solution. The results show that when the temperature is increased, protonated amino groups in the chitosan molecules can dissociate to form hydrogen ions, thereby resulting in a decrease in pH, and the free amino groups can complex with metal ions, thereby crosslinking to form the highly elastic thermoreversible hydrogel. The heat-setting gel is clear and transparent, and can be recycled for more than 100 times. The present thermoreversible gel is characterized in that the gel is changed into gel from sol along with the reduction of temperature, and the gel is changed into sol from gel when being heated again, so that the thermoreversible gel has thermoreversibility.
Drawings
FIG. 1 is a photograph of different hydrogels.
FIG. 2 is a graph of the effect of temperature on the pH of the gel precursor solution.
FIG. 3 is a graph of rheology versus temperature for chitosan-nickel ion solutions.
Detailed Description
Examples of embodiments of the present invention are provided for more fully explaining the practice of the present invention, and are merely illustrative of the present invention and do not limit the scope of the present invention.
Example 1:
dissolving chitosan with deacetylation degree of more than 95% in acetic acid solution with volume concentration of 1% to obtain chitosan solution with concentration of 2.0 wt%, taking 2mL solution, slowly adding 30 μl NaOH solution with concentration of 0.5M under stirring, stirring uniformly, and adding 400 μl Ni (NO) with concentration of 0.5M 3 ) 2 The solution is stirred uniformly. And then heating to about 95 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature, the gel slowly changed back to the original solution.
Example 2:
dissolving chitosan with deacetylation degree of more than 95% in acetic acid solution with volume concentration of 1% to obtain chitosan solution with concentration of 2.0 wt%, taking 3 mL solution, slowly adding 15 μl NaOH solution with concentration of 0.5M under stirring, stirring uniformly, and adding 600 μl Cu (NO) with concentration of 0.5M 3 ) 2 The solution is stirred uniformly. And then heating to about 85 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature, the gel slowly changed back to the original solution.
Example 3:
dissolving chitosan with deacetylation degree of more than 95% in acetic acid solution with volume concentration of 1% to obtain chitosan solution with concentration of 2.0 wt%, taking 2mL solution, slowly adding 100 μl NaOH solution with concentration of 0.5M under stirring, stirring uniformly, and adding 400 μl Zn (NO) with concentration of 0.5M 3 ) 2 The solution is stirred uniformly. And then heating to about 95 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature, the gel slowly changed back to the original solution.
Example 4:
dissolving chitosan with deacetylation degree of more than 95% in acetic acid solution with volume concentration of 1% to obtain chitosan solution with concentration of 2.0 wt%, mixing 3 mL solution, slowly adding 300 μl NaOH solution with concentration of 0.5M under stirring,stirred evenly, then 600 mu L of Co (NO) with the concentration of 0.5M is added 3 ) 2 The solution is stirred uniformly. And then heating to about 90 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature, the gel slowly changed back to the original solution.
Example 5:
dissolving chitosan with deacetylation degree of more than 95% in 1 mol% hydrochloric acid solution to obtain 1.0 wt% chitosan solution, collecting 2mL solution, slowly adding 80 μl NaOH solution with concentration of 0.5M under stirring, adding 200 μl Zn (NO) with concentration of 0.5M 3 ) 2 The solution is stirred uniformly. And then heating to about 90 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature, the gel slowly changed back to the original solution.
Example 6:
dissolving chitosan with deacetylation degree of more than 95% in 1 mol% hydrochloric acid solution to obtain 3 wt% chitosan solution, taking 2mL of the solution, slowly adding 200 μL of 0.5M NaOH solution under stirring, and adding 600 μL of 0.5M Ni (NO) 3 ) 2 The solution is stirred uniformly. And then heating to about 95 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature, the gel slowly changed back to the original solution.
FIG. 1 is a photograph of a gel obtained according to the present invention.
The mechanism analysis of the invention: FIG. 2 is a diagram for the mechanism discussion and explanation of the present invention, wherein CS is chitosan, UP is heating UP, and Down is cooling down, and hydrochloric acid is used to dissolve chitosan. Fig. 2 is merely illustrative of the mechanism of the present invention. In fig. 2, the amino groups on chitosan are mainly present as ammonium salts at 40 ℃ in chitosan (protonated) solution, and the acting force of the ammonium salts and nickel ions is very low. The solution is thus in a flowing state, at which point the pH is about 3.5. With the gradual rise of the temperature, the ammonium salt on the protonated chitosan molecule is dissociated to generate free amino and H + ，H + The pH of the solution is lowered, and at the same time, free amino groups can form strong complexation with nickel ions in the solution, so that a dynamic molecular network is formed by crosslinking. When nickel ions are added and the temperature risesWhen the critical point is reached, the cross-linking points formed by complexing nickel ions and amino groups are enough, and the high molecular network binds water molecules to generate the high-elastic hydrogel. When the temperature is reduced, the process is completely reversible, and free H + Recombined with amino groups to form ammonium salts. And nickel ions are released again into the solution, causing the gel to change into a solution state.
FIG. 3 is a graph of the rheology of chitosan-nickel ion solution versus temperature. At normal temperature, the protonated chitosan has weak acting force with nickel ions and can not form cross-linking, so the protonated chitosan is in a solution state. At this time, the loss modulus (G ") of the sample is greater than the storage modulus (G'). When the temperature is raised to a certain critical point (about 68 ℃), the ammonium salt on the chitosan molecule dissociates and the free amino groups form strong cross-linking reactions with nickel ions, thus forming a gel. At this time, the storage modulus (G') of the sample is larger than the loss modulus (G).
Claims (4)
1. A preparation method of heat-setting chitosan hydrogel is characterized in that: the preparation method comprises the following steps: dissolving chitosan with deacetylation degree of more than 95% in acetic acid solution with volume concentration of 1% to obtain chitosan solution with concentration of 2.0 wt%, mixing 2mL solution, adding 30 μl NaOH solution with concentration of 0.5M, stirring, adding 400 μl Ni (NO) with concentration of 0.5M 3 ) 2 And (3) uniformly stirring the solution, and then heating to 95 ℃ to obtain the heat-setting chitosan hydrogel.
2. The method for preparing the heat-setting chitosan hydrogel according to claim 1, wherein the method comprises the following steps: and cooling the heat-set chitosan hydrogel to normal temperature, and changing the heat-set chitosan hydrogel into sol with good fluidity.
3. The method for preparing the heat-setting chitosan hydrogel according to claim 1, wherein the method comprises the following steps: the gel forming time of the heat-setting chitosan hydrogel is less than or equal to 3min.
4. The method for preparing the heat-setting chitosan hydrogel according to claim 1, wherein the method comprises the following steps: the heat-setting chitosan hydrogel is clear and transparent, and the circulation times are more than 100 times.
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| US8835514B2 (en) * | 2004-03-22 | 2014-09-16 | Laboratoire Medidom S.A. | Pseudo-thermosetting neutralized chitosan composition forming a hydrogel and a process for producing the same |
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| CN111171346A (en) * | 2020-01-23 | 2020-05-19 | 同济大学 | Chitosan hydrogel material and preparation method and application thereof |
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