CN111333870A - Self-repairable chitosan hydrogel and preparation method thereof - Google Patents
Self-repairable chitosan hydrogel and preparation method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- RAFNCPHFRHZCPS-UHFFFAOYSA-N di(imidazol-1-yl)methanethione Chemical compound C1=CN=CN1C(=S)N1C=CN=C1 RAFNCPHFRHZCPS-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 125000004427 diamine group Chemical group 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 12
- 231100000053 low toxicity Toxicity 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
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- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000013268 sustained release Methods 0.000 abstract description 2
- 239000012730 sustained-release form Substances 0.000 abstract description 2
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- IFZOPNLVYZYSMQ-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethoxy]ethanamine Chemical compound NCCOCCOCCOCCOCCN IFZOPNLVYZYSMQ-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
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- 239000004202 carbamide Substances 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/02—Polyureas
-
- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/02—Polyureas
Abstract
The invention discloses a self-repairing chitosan hydrogel and a preparation method thereof. The invention mixes and reacts a diimidazole compound and diamine to obtain a pre-reaction solution containing thiourea groups and urea groups, and further reacts with chitosan, hydrogen bond groups such as thiourea groups and urea groups are introduced into a high molecular chain segment of the chitosan hydrogel, and self-repair of the material is realized by means of the breakage and recombination of hydrogen bonds in molecules or between molecules, so that the chitosan hydrogel material has a better self-repair function. The self-repairing chitosan hydrogel has the advantages of high self-repairing efficiency, simple preparation process and low cost. The chitosan hydrogel prepared by the invention has the advantages of low toxicity, biodegradability and the like, and can be applied to the fields of drug sustained-release materials, tissue engineering scaffolds, medical dressings, printing and dyeing wastewater treatment and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogel, and particularly relates to self-repairable chitosan hydrogel and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Chitosan (CTS) is a natural organic high molecular polysaccharide from shrimp and crab shells, has good biocompatibility, has the biological functions of collagen in higher animal tissues and cellulose in higher plant tissues, has good adaptability to animals and plants, has affinity with organisms on the cellular level, and has low possibility of generating antigen. Has biological activities of resisting inflammation, inhibiting bacteria, promoting wound repair and the like, and plays a role in stopping bleeding through various ways.
The chitosan hydrogel has the advantages of low toxicity, biodegradability and the like, and has good application prospects in the fields of drug slow-release materials, tissue engineering scaffolds, medical dressings, printing and dyeing wastewater treatment and the like. However, the current chitosan hydrogel still has some problems, such as poor mechanical properties, easy deformation and breakage, unrecoverable damage and short service life, which greatly limits the application of the chitosan hydrogel. The development of chitosan hydrogel with self-repairing function becomes a new research direction. However, the chitosan hydrogel with self-repairing property has some problems which are difficult to ignore, such as poor self-repairing property, inconvenient preparation method, high preparation cost and the like.
Disclosure of Invention
The invention aims to: provides a chitosan hydrogel with a self-repairing function and a preparation method thereof.
The object of the invention is achieved by:
a self-repairable chitosan hydrogel comprises a chitosan cross-linked copolymer, which comprises a chitosan cross-linked copolymer and a chitosan hydrogel, wherein the mass ratio of the chitosan cross-linked copolymer to the chitosan hydrogel is 1: (0.1-10): (0.1-10) component A, component B and component C; wherein the component A is chitosan aqueous solution; the component B is a diamine aqueous solution; the component C is a diimidazole compound aqueous solution;
the number average molecular weight of chitosan in the component A is less than or equal to 100000 g/mol;
the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole;
the diamine is at least one of the substances shown in the following structural formula:
wherein m is 1-200; n is 0 to 5; t is 1-5; k is 1-16;
the mass percentage concentration of the component A chitosan aqueous solution is 1-98%; the component B is a diamine aqueous solution with the mass percentage concentration of 0-100%; the mass percentage concentration of the C component diimidazole compound aqueous solution is 1-100%.
A preparation method of a self-repairable chitosan hydrogel comprises the following steps:
(1) preparation of reaction solution
Dissolving chitosan in deionized water to obtain a component A chitosan aqueous solution; dissolving diamine in deionized water to obtain a diamine aqueous solution of a component B; dissolving a diimidazole compound in deionized water to obtain a C component diimidazole compound aqueous solution;
(2) preparation of the Pre-polymerization liquid
Mixing the components in a mass ratio of 1: (0.1-10) mixing the component B and the component C, uniformly stirring, and reacting at 10-80 ℃ for 1-12 h to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing the components in a mass ratio of 1: and (3) mixing the (0.1-10) prepolymerization solution with the component A, uniformly stirring, and reacting for 1-12 h at 10-80 ℃ to obtain the self-repairing chitosan hydrogel.
In order to realize the self-repairing function of the chitosan hydrogel, the invention comprises the following steps:
the reaction ratio of diamine and N, N' -thiocarbonyl diimidazole is controlled, and thiourea-containing groups can be introduced into the prepolymerization liquid as shown in the following;
wherein:
represents a diamine.
The reaction ratio of diamine and N, N' -carbonyl diimidazole is controlled, and urea-containing groups can be introduced into the prepolymerization liquid as shown in the following;
wherein:
represents a diamine.
The reaction ratio of diamine, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole is controlled, and urea-containing groups and thiourea groups can be simultaneously introduced into the prepolymerization liquid, as shown in the following;
wherein:
represents a diamine.
And (2) mixing and reacting a diimidazole compound and diamine to obtain a prepolymerization solution containing thiourea groups and urea groups, and further reacting with chitosan, so that hydrogen bond groups such as thiourea groups and urea groups are introduced into a chitosan hydrogel polymer chain segment, and self-repair of the material is realized by means of breakage and recombination of hydrogen bonds in molecules or between molecules, so that the chitosan hydrogel material has a better self-repair function. The principle of the hydrogen bond action inside the chitosan hydrogel material containing thiourea groups, urea groups and other hydrogen bond groups is as follows:
meanwhile, the formed hydrogen bond groups such as thiourea-containing groups, urea groups and the like can also form a hydrogen bond structure with a hydrogen bond donor/acceptor of the chitosan, so that the hydrogen bond function of the system is further enhanced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention mixes and reacts a diimidazole compound and diamine to obtain a pre-reaction solution containing thiourea groups and urea groups, and further reacts with chitosan, hydrogen bond groups such as thiourea groups and urea groups are introduced into a high molecular chain segment of the chitosan hydrogel, and self-repair of the material is realized by means of the breakage and recombination of hydrogen bonds in molecules or between molecules, so that the chitosan hydrogel material has a better self-repair function.
2. The self-repairing chitosan hydrogel has the advantages of high self-repairing efficiency, simple preparation process and low cost.
3. The chitosan hydrogel prepared by the invention has the advantages of low toxicity, biodegradability and the like, and can be applied to the fields of drug sustained-release materials, tissue engineering scaffolds, medical dressings, printing and dyeing wastewater treatment and the like.
Drawings
FIG. 1 is a picture of the self-healing process of the hydrogel of the chitosan dressing of example 1.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Preparation of reaction solution
Dissolving chitosan (with average molecular weight of 2000 g/mol) in deionized water to obtain a component A chitosan aqueous solution with mass percentage concentration of 3%; dissolving 1, 2-bis (2-aminoethoxy) ethane in deionized water to obtain a B component 1, 2-bis (2-aminoethoxy) ethane aqueous solution with the mass percentage concentration of 8%; dissolving N, N '-thiocarbonyl diimidazole in deionized water to obtain a C component N, N' -thiocarbonyl diimidazole water solution with the mass percentage concentration of 4%;
(2) preparation of the Pre-polymerization liquid
Mixing 100g of the component B and 100g of the component C, uniformly stirring, and reacting for 8 hours at 40 ℃ to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing 100g of the prepolymerization solution and 100g of the component A, uniformly stirring, and reacting for 6 hours at 40 ℃ to obtain self-repairing chitosan hydrogel;
as shown in the attached figure 1, the obtained self-repairable chitosan hydrogel material is disconnected and contacted again, and the hydrogel material can heal and repair within 2 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Through detection, the prepared self-repairing chitosan hydrogel can be used for treating various heavy metal ions (such as Cd)2+，Hg2+，Pb2+Etc.) has better selective adsorption performance, and the removal rate can reach more than 90 percent. Tests show that the prepared self-repairable chitosan hydrogel has a very high adsorption rate on heavy metals and very good adsorption kinetics, and can reach balance within 10min basically.
Through detection, the prepared self-repairable chitosan hydrogel can be finally degraded after being placed in an outdoor environment for 3 months.
Through detection, in vitro cytotoxicity test on the prepared self-repairable chitosan hydrogel shows that tissue fibroblasts can grow and proliferate on the hydrogel, and low toxicity and good affinity to cells are embodied.
Example 2
(1) Preparation of reaction solution
Dissolving chitosan (with the average molecular weight of 5000 g/mol) in deionized water to obtain a component A chitosan aqueous solution with the mass percentage concentration of 10%; dissolving triethylene glycol bis (2-aminoethyl) ether in deionized water to obtain a B component triethylene glycol bis (2-aminoethyl) ether aqueous solution with the mass percentage concentration of 10%; dissolving N, N '-thiocarbonyl diimidazole in deionized water to obtain a C component N, N' -thiocarbonyl diimidazole water solution with the mass percentage concentration of 10%;
(2) preparation of the Pre-polymerization liquid
Mixing 100g of the component B and 5g of the component C, uniformly stirring, and reacting for 6 hours at 40 ℃ to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing 100g of the pre-polymerization solution and 3g of the component A, uniformly stirring, and reacting for 7 hours at the temperature of 30 ℃ to obtain the self-repairing chitosan hydrogel;
the obtained self-repairing chitosan hydrogel material is disconnected and contacted again, and the hydrogel material can be healed and repaired within 1 minute and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Through detection, the prepared self-repairing chitosan hydrogel can be used for treating various heavy metal ions (such as Cd)2+，Hg2+，Pb2+Etc.) has better selective adsorption performance, and the removal rate can reach more than 90 percent. Tests show that the prepared self-repairable chitosan hydrogel has a very high adsorption rate on heavy metals and very good adsorption kinetics, and can reach balance within 10min basically.
Through detection, the prepared self-repairable chitosan hydrogel can be finally degraded after being placed in an outdoor environment for 3 months.
Through detection, in vitro cytotoxicity test on the prepared self-repairable chitosan hydrogel shows that tissue fibroblasts can grow and proliferate on the hydrogel, and low toxicity and good affinity to cells are embodied.
Example 3
(1) Preparation of reaction solution
Dissolving chitosan (with average molecular weight of 80000 g/mol) in deionized water to obtain a component A chitosan aqueous solution with mass percentage concentration of 50%; dissolving ethylene glycol mono (2-aminoethyl) ether in deionized water to obtain a B component ethylene glycol mono (2-aminoethyl) ether aqueous solution with the mass percentage concentration of 1%; dissolving N, N '-thiocarbonyl diimidazole in deionized water to obtain a C component N, N' -thiocarbonyl diimidazole water solution with the mass percentage concentration of 5%;
(2) preparation of the Pre-polymerization liquid
Mixing 100g of the component B and 100g of the component C, uniformly stirring, and reacting for 5 hours at the temperature of 30 ℃ to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing 100g of the pre-polymerization solution with 50g of the component A, uniformly stirring, and reacting for 6 hours at 40 ℃ to obtain the self-repairing chitosan hydrogel;
the obtained self-repairing chitosan hydrogel material is disconnected and contacted again, and the hydrogel material can be healed and repaired within 5 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Through detection, the prepared self-repairing chitosan hydrogel can be used for treating various heavy metal ions (such as Cd)2+，Hg2+，Pb2+Etc.) has better selective adsorption performance, and the removal rate can reach more than 95 percent. Tests show that the prepared self-repairable chitosan hydrogel has a very high adsorption rate on heavy metals and very good adsorption kinetics, and can reach balance within 10min basically.
Through detection, the prepared self-repairable chitosan hydrogel can be finally degraded after being placed in an outdoor environment for 6 months.
Through detection, in vitro cytotoxicity test on the prepared self-repairable chitosan hydrogel shows that tissue fibroblasts can grow and proliferate on the hydrogel, and low toxicity and good affinity to cells are embodied.
Example 4
(1) Preparation of reaction solution
Dissolving chitosan (average molecular weight is 40000 g/mol) in deionized water to obtain a component A chitosan aqueous solution with mass percentage concentration of 10%; dissolving ethylenediamine in deionized water to obtain a component B ethylenediamine aqueous solution with the mass percentage concentration of 5%; dissolving N, N '-carbonyldiimidazole in deionized water to obtain a C component N, N' -carbonyldiimidazole aqueous solution with the mass percentage concentration of 5%;
(2) preparation of the Pre-polymerization liquid
Mixing 100g of the component B and 60g of the component C, uniformly stirring, and reacting for 1h at 80 ℃ to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing 100g of prepolymerization liquid and 40g of component A, uniformly stirring, and reacting for 12h at 30 ℃ to obtain self-repairing chitosan hydrogel;
the obtained self-repairing chitosan hydrogel material is disconnected and contacted again, and the hydrogel material can be healed and repaired within 6 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Through detection, the prepared self-repairing chitosan hydrogel can be used for treating various heavy metal ions (such as Cd)2+，Hg2+，Pb2+Etc.) has better selective adsorption performance, and the removal rate can reach more than 99 percent. Tests show that the prepared self-repairable chitosan hydrogel has a very high adsorption rate on heavy metals and very good adsorption kinetics, and can reach balance within 10min basically.
Through detection, the prepared self-repairable chitosan hydrogel can be finally degraded after being placed in an outdoor environment for 1 month.
Through detection, in vitro cytotoxicity test on the prepared self-repairable chitosan hydrogel shows that tissue fibroblasts can grow and proliferate on the hydrogel, and low toxicity and good affinity to cells are embodied.
Example 5
(1) Preparation of reaction solution
Dissolving chitosan (with average molecular weight of 1000 g/mol) in deionized water to obtain a component A chitosan aqueous solution with mass percentage concentration of 98%; dissolving hexamethylene diamine in deionized water to obtain a component B hexamethylene diamine water solution with the mass percentage concentration of 10%; dissolving N, N '-carbonyldiimidazole in deionized water to obtain a C component N, N' -carbonyldiimidazole aqueous solution with the mass percentage concentration of 4%;
(2) preparation of the Pre-polymerization liquid
Mixing 100g of the component B and 50g of the component C, uniformly stirring, and reacting for 1h at 80 ℃ to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing 100g of prepolymerization liquid and 5g of component A, uniformly stirring, and reacting at 10 ℃ for 12h to obtain self-repairing chitosan hydrogel;
the obtained self-repairable chitosan hydrogel material is cut off and contacted again, and the hydrogel material can be healed and repaired within 10 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Through detection, the prepared self-repairing chitosan hydrogel can be used for treating various heavy metal ions (such as Cd)2+，Hg2+，Pb2+Etc.) has better selective adsorption performance, and the removal rate can reach more than 98%. Tests show that the prepared self-repairable chitosan hydrogel has a very high adsorption rate on heavy metals and very good adsorption kinetics, and can reach balance within 10min basically.
Through detection, the prepared self-repairable chitosan hydrogel can be finally degraded after being placed in an outdoor environment for 3 months.
Through detection, in vitro cytotoxicity test on the prepared self-repairable chitosan hydrogel shows that tissue fibroblasts can grow and proliferate on the hydrogel, and low toxicity and good affinity to cells are embodied.
Example 6
(1) Preparation of reaction solution
Dissolving chitosan (with average molecular weight of 100000 g/mol) in deionized water to obtain a component A chitosan aqueous solution with mass percentage concentration of 1%; dissolving N, N '-carbonyldiimidazole in deionized water to obtain a C component N, N' -carbonyldiimidazole aqueous solution with the mass percentage concentration of 1%;
(2) preparation of self-repairable chitosan hydrogel
Mixing 100g of the component B and 1g of the component A, uniformly stirring, and reacting for 1h at 80 ℃ to obtain the self-repairing chitosan hydrogel;
the obtained self-repairable chitosan hydrogel material is disconnected and contacted again, and the hydrogel material can be healed and repaired within 20 minutes and can be stretched. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Through detection, the prepared self-repairing chitosan hydrogel can be used for treating various heavy metal ions (such as Cd)2+，Hg2+，Pb2+Etc.) has better selective adsorption performance, and the removal rate can reach more than 90 percent. Tests show that the prepared self-repairable chitosan hydrogel has a very high adsorption rate on heavy metals and very good adsorption kinetics, and can reach balance within 10min basically.
Through detection, the prepared self-repairable chitosan hydrogel can be finally degraded after being placed in an outdoor environment for 3 months.
Through detection, in vitro cytotoxicity test on the prepared self-repairable chitosan hydrogel shows that tissue fibroblasts can grow and proliferate on the hydrogel, and low toxicity and good affinity to cells are embodied.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (2)
1. A self-repairable chitosan hydrogel comprises a chitosan cross-linked copolymer, and is characterized in that: comprises the following components in percentage by mass of 1: (0.1-10): (0.1-10) component A, component B and component C; wherein the component A is chitosan aqueous solution; the component B is a diamine aqueous solution; the component C is a diimidazole compound aqueous solution;
the number average molecular weight of chitosan in the component A is less than or equal to 100000 g/mol;
the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole;
the diamine is at least one of the substances shown in the following structural formula:
wherein m is 1-200; n is 0 to 5; t is 1-5; k is 1-16;
the mass percentage concentration of the component A chitosan aqueous solution is 1-98%;
the component B is a diamine aqueous solution with the mass percentage concentration of 0-100%;
the mass percentage concentration of the C component diimidazole compound aqueous solution is 1-100%.
2. The preparation method of the self-repairable chitosan hydrogel of claim 1, characterized by comprising the following steps:
(1) preparation of reaction solution
Dissolving chitosan in deionized water to obtain a component A chitosan aqueous solution;
dissolving diamine in deionized water to obtain a diamine aqueous solution of a component B;
dissolving a diimidazole compound in deionized water to obtain a C component diimidazole compound aqueous solution;
(2) preparation of the Pre-polymerization liquid
Mixing the components in a mass ratio of 1: (0.1-10) mixing the component B and the component C, uniformly stirring, and reacting at 10-80 ℃ for 1-12 h to obtain a pre-polymerization solution;
(3) preparation of self-repairable chitosan hydrogel
Mixing the components in a mass ratio of 1: and (3) mixing the (0.1-10) prepolymerization solution with the component A, uniformly stirring, and reacting for 1-12 h at 10-80 ℃ to obtain the self-repairing chitosan hydrogel.
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| CN202010262157.7A CN111333870A (en) | 2020-04-06 | 2020-04-06 | Self-repairable chitosan hydrogel and preparation method thereof |
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| CN112280056A (en) * | 2020-11-06 | 2021-01-29 | 湖南科技大学 | Preparation method of repairable graphene oxide material based on hydrogen bond effect |
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