CN114805859A - Preparation method of heat-setting chitosan hydrogel - Google Patents
Preparation method of heat-setting chitosan hydrogel Download PDFInfo
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- CN114805859A CN114805859A CN202210679092.5A CN202210679092A CN114805859A CN 114805859 A CN114805859 A CN 114805859A CN 202210679092 A CN202210679092 A CN 202210679092A CN 114805859 A CN114805859 A CN 114805859A
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- 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
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A preparation method of a heat-setting chitosan hydrogel comprises the following steps: s1: dissolving chitosan with deacetylation degree of more than 95% in 1% acetic acid solution or 1% hydrochloric acid solution to obtain (1-3) wt% chitosan solution; s2: adding NaOH solution into chitosan solution under stirring, and stirring uniformly, wherein the concentration of NaOH added dropwise into each milliliter of chitosan solution of 1 wt% is (1.25-25) x 10 ‑6 mol; s3: adding a metal nitrate solution to the system obtained in the step S2; s4: and (4) heating the system obtained in the step S3 to 80-100 ℃ to obtain the heat-set chitosan hydrogel. The invention relates to less reports of thermally reversible gel which is formed into gel by heating and becomes sol by cooling, and the hydrogel is formed in a heating state, thereby further exploiting the application scope of the hydrogelAnd (3) removing the solvent.
Description
Technical Field
The invention relates to a preparation method of hydrogel, in particular to a preparation method of heat-setting chitosan hydrogel, belonging 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, stimulation responsiveness, easy functionalization and the like, and has wide application in the fields of biochemistry, medical sanitation, agriculture, environmental protection and the like. A thermoreversible gel is a gel that can be melted and reformed according to temperature. Most thermally reversible gels are characterized by thermal reversibility, in which the gel changes from sol to gel as the temperature decreases and then changes from gel to sol when heated again. Hydrogels can be classified as natural hydrogels and synthetic hydrogels, depending on the source of the gel molecules. The materials of the artificial hydrogel can be divided into natural macromolecules and artificial molecules. Artificially synthesized molecules are often obtained by petrochemical extraction or organic synthesis polymerization, and have complicated preparation process, high cost and non-regeneration. Therefore, the development of hydrogels based on naturally renewable polymers is of great interest.
Disclosure of Invention
The object of the present invention is to develop heat-settable hydrogels based on naturally renewable macromolecules.
In order to realize the purpose of the invention, the following technical scheme is adopted: a preparation method of heat-setting chitosan hydrogel comprises the following steps:
s1: dissolving chitosan with deacetylation degree of more than 95% in 1% acetic acid solution or 1% hydrochloric acid solution to prepare (1-3) wt% chitosan solution with viscosity of 100-200 mpa.s;
s2: adding NaOH solution into chitosan solution under stirring, and stirring uniformly, wherein the concentration of NaOH added dropwise into each milliliter of chitosan solution of 1 wt% is (1.25-25) x 10 -6 mol, the concentration of NaOH solution is 0.4-0.7M;
s3: adding a nitrate metal salt 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 solution contains metal nitrate solution with concentration of 0.4-0.7M, and chitosan solution with concentration of 2.0 wt% per ml with nitrate amount of (0.9-1.1) × 10 -4 mol；
S4: and (4) heating the system obtained in the step S3 to 80-100 ℃ to obtain the heat-set chitosan hydrogel.
Further, the method comprises the following steps of; and (4) cooling the heat-set chitosan hydrogel obtained in the step (S4) to normal temperature, so that the heat-set chitosan hydrogel is changed into sol with good fluidity.
Further, the method comprises the following steps of; the nitrate metal salt solution is Ni (NO) 3 ) 2 The solution is prepared by the following method: dissolving chitosan with deacetylation degree of above 95% in 1% acetic acid solution to obtain 2.0 wt% chitosan solution, adding 30 μ L NaOH solution with concentration of 0.5M into 2mL of the prepared solution, stirring, adding 400 μ L Ni (NO) with concentration of 0.5M 3 ) 2 And uniformly stirring the solution, and then heating to 95 ℃ to obtain the heat-setting chitosan hydrogel.
Further, the method comprises the following steps of; the gelling time of the heat-setting chitosan hydrogel is less than or equal to 3 min.
Further, the method comprises the following steps of; the heat-setting chitosan hydrogel is clear and transparent, and the circulating times are more than 100.
The invention has the positive and beneficial technical effects that: chitosan is an alkaline aminopolysaccharide formed from natural chitin by deacetylation reaction, and is widely present in nature. The invention takes natural chitosan as raw material, acetic acid and hydrochloric acid as solvent, and metal ions are added, and the completely reversible heat setting hydrogel is prepared by raising the temperature of the solution. The result shows that when the temperature is increased, the protonated amino groups in the chitosan molecules can be dissociated into hydrogen ions, so that the pH is reduced, and the free amino groups can be complexed with metal ions, so that the high-elasticity thermally reversible hydrogel is formed by crosslinking. The heat-setting gel is clear and transparent, and can be circulated for more than 100 times. The thermally reversible gel is a gel which can be melted and modified according to temperature, and the existing thermally reversible gel is characterized in that the gel is changed from sol to gel along with the reduction of the temperature, and the gel is changed into the sol from the gel when being heated again, so that the thermally reversible gel has thermal reversibility.
Drawings
FIG. 1 is a photograph of different hydrogels.
FIG. 2 is a graph of the effect of temperature on the pH of a gel precursor solution.
FIG. 3 is a graph of rheology versus temperature for chitosan-nickel ion solutions.
Detailed Description
In order to more fully explain the implementation of the present invention, the implementation examples of the present invention are provided, which 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 above 95% in 1% acetic acid solution to obtain 2.0 wt% chitosan solution, adding 2mL of the prepared solution, slowly adding 30 μ L of 0.5M NaOH solution under stirring, adding 400 μ L of 0.5M Ni (NO) 3 ) 2 And (5) uniformly stirring the solution. Then heating to about 95 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature the gel slowly returned to the original solution.
Example 2:
dissolving chitosan with deacetylation degree of more than 95% in 1% acetic acid solution to obtain 2.0 wt% chitosan solution, adding 3 mL of the prepared solution, slowly adding 15 μ L of 0.5M NaOH solution under stirring, adding 600 μ L of 0.5M Cu (NO) 3 ) 2 And (5) uniformly stirring the solution. Then heating to about 85 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature the gel slowly returned to the original solution.
Example 3:
dissolving chitosan with deacetylation degree of above 95% in acetic acid solution with volume concentration of 1%Preparing 2.0 wt% chitosan solution, collecting 2mL of the prepared solution, slowly adding 100 μ L of 0.5M NaOH solution under stirring, adding 400 μ L of 0.5M Zn (NO) 3 ) 2 And (5) uniformly stirring the solution. Then heating to about 95 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature the gel slowly returned to the original solution.
Example 4:
dissolving chitosan with deacetylation degree of more than 95% in 1% acetic acid solution to obtain 2.0 wt% chitosan solution, adding 3 mL of the prepared solution, slowly adding 300 μ L of 0.5M NaOH solution under stirring, adding 600 μ L of 0.5M Co (NO) 3 ) 2 And (5) uniformly stirring the solution. Then heating to about 90 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature the gel slowly returned to the original solution.
Example 5:
dissolving chitosan with deacetylation degree of above 95% in 1% hydrochloric acid solution to obtain 1.0 wt% chitosan solution, adding 2mL of the prepared solution, slowly adding 80 μ L of 0.5M NaOH solution under stirring, adding 200 μ L of 0.5M Zn (NO) 3 ) 2 And (5) uniformly stirring the solution. Then heating to about 90 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature the gel slowly returned to the original solution.
Example 6:
dissolving chitosan with deacetylation degree of more than 95% in 1% hydrochloric acid solution to obtain 3 wt% chitosan solution, adding 2mL of the prepared solution, slowly adding 200 μ L of 0.5M NaOH solution under stirring, adding 600 μ L of 0.5M Ni (NO) 3 ) 2 And (5) uniformly stirring the solution. Then heating to about 95 ℃ to obtain the clear transparent high-elastic hydrogel. After cooling at room temperature the gel slowly returned to the original solution.
FIG. 1 is a photograph of a gel obtained by the present invention.
Mechanism analysis of the present invention: FIG. 2 is a schematic diagram for explaining and discussing the mechanism of the present inventionIn the figure, CS is chitosan, UP is temperature rise and down is temperature decrease, and hydrochloric acid is adopted to dissolve the chitosan. Fig. 2 is only for illustrating the mechanism of the present invention. In FIG. 2, the amino groups on chitosan (protonated) are mainly present as ammonium salts at 40 deg.C, and the action force of the ammonium salts and nickel ions is very low. The solution was thus in a fluid state, at which the pH was 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 value of the solution is reduced, and meanwhile, the free amino can form strong complexation with nickel ions in the solution, and a dynamic molecular network is formed by crosslinking. When nickel ions are added and the temperature is raised to a certain critical point, enough crosslinking points are formed by complexing of the nickel ions and amino groups, and a 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 + And the ammonium salt is formed by recombining with the amino. And the nickel ions are released into the solution again to convert the gel into a solution state.
FIG. 3 is a graph of rheology versus temperature for chitosan-nickel ion solutions. At normal temperature, the protonized chitosan has weak action force with nickel ions, can not form cross linking, and 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 group forms a strong cross-linking reaction with the nickel ion, thereby forming a gel. At this time, the storage modulus (G') of the sample is larger than the loss modulus (G).
Claims (5)
1. A preparation method of heat-setting chitosan hydrogel is characterized by comprising the following steps:
s1: dissolving chitosan with deacetylation degree of more than 95% in 1% acetic acid solution or 1% hydrochloric acid solution to prepare (1-3) wt% chitosan solution with viscosity of 100-200 mpa.s;
s2 adding NaOH solution into the chitosan solution under stirring, and stirring uniformly, wherein the concentration of NaOH added dropwise into each milliliter of 1 wt% of chitosan solution is (1.25-2)5）×10 -6 mol, the concentration of NaOH solution is 0.4-0.7M;
s3: adding a nitrate metal salt solution into the system obtained in the step S2, and uniformly stirring; the metal nitrate solution comprises Ni (NO3)2, Cu (NO3)2, Zn (NO3)2, Cd (NO3)2 and Co (NO3)2 solutions, the concentration of the metal nitrate solution is 0.4-0.7M, and the nitrate amount added into the chitosan solution with the concentration of 2.0 wt% per milliliter is (0.9-1.1) multiplied by 10 -4 mol；
S4: and (4) heating the system obtained in the step S3 to 80-100 ℃ to obtain the heat-set chitosan hydrogel.
2. The method for preparing a heat-set chitosan hydrogel according to claim 1, wherein: and (4) cooling the heat-set chitosan hydrogel obtained in the step (S4) to normal temperature, so that the heat-set chitosan hydrogel is changed into sol with good fluidity.
3. The method for preparing a heat-set chitosan hydrogel as claimed in claim 1, wherein: the nitrate metal salt solution is Ni (NO3)2 solution, and the preparation method comprises the following steps: dissolving chitosan with deacetylation degree of above 95% in 1% acetic acid solution to obtain 2.0 wt% chitosan solution, adding 30 μ L NaOH solution with concentration of 0.5M into 2mL of the prepared solution, stirring, adding 400 μ L Ni (NO) with concentration of 0.5M 3 ) 2 And uniformly stirring the solution, and then heating to 95 ℃ to obtain the heat-setting chitosan hydrogel.
4. The method for preparing a heat-set chitosan hydrogel as claimed in claim 3, wherein: the gelling time of the heat-setting chitosan hydrogel is less than or equal to 3 min.
5. The method for preparing a heat-set chitosan hydrogel as claimed in claim 3, wherein: the heat-setting chitosan hydrogel is clear and transparent, and the circulating times are more than 100.
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