CN112940287B - Shape memory chitosan hydrogel and preparation method thereof - Google Patents
Shape memory chitosan hydrogel and preparation method thereof Download PDFInfo
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- CN112940287B CN112940287B CN202110152190.9A CN202110152190A CN112940287B CN 112940287 B CN112940287 B CN 112940287B CN 202110152190 A CN202110152190 A CN 202110152190A CN 112940287 B CN112940287 B CN 112940287B
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- 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
Abstract
The invention discloses shape memory chitosan hydrogel and a preparation method thereof, firstly, chitosan is dissolved under an acidic condition to obtain a chitosan solution; then stirring the chitosan solution at a high speed by using a homogenizer, simultaneously deprotonating chitosan by using an alkali liquor to convert the chitosan into a gel state, finishing primary assembly, and stirring to obtain a stable white milky chitosan fiber bundle suspension; adding a cross-linking agent while stirring to obtain a cross-linked chitosan fiber bundle suspension; concentrating to obtain concentrated suspension, injecting the concentrated suspension into a mold with a required shape, and standing for a period of time to enable the chitosan to fully react with the cross-linking agent; then placing the frozen body in a refrigerator for freezing to obtain a frozen body, and performing secondary assembly by ice crystal growth under the low-temperature condition; and (3) unfreezing the frozen body to obtain the chitosan hydrogel with the shape memory function. The chitosan hydrogel prepared by the invention has the advantages of good mechanical property, good water absorption property, simple preparation process and easy large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of material chemistry and natural polymers, relates to a gel material, and particularly relates to shape memory chitosan hydrogel and a preparation method thereof.
Background
The chitosan is a natural high molecular polymer with abundant resources and wide sources in the nature, and has the excellent characteristics of renewability, biodegradability, biocompatibility, antibacterial property, multifunctional group reaction activity, wound healing promotion and the like. The hydrogel is a flexible substance with a three-dimensional network structure and rich water content, has excellent water absorption and retention property and gel stability, and can be used as a good matrix, carrier or framework of a functional soft material. Based on the advantages, the gel, the stent, the sponge and the like developed on the basis of chitosan are widely applied to the fields of adsorption recovery, oil-water separation and numerous biological and medical purposes, including medical hemostatic dressings, drug slow release materials, tissue engineering carrier materials, medical absorbable materials, gene transduction carriers, medical treatment, drug development and the like. In addition, as a flexible and smart material having multifunctional group reactivity, it also has an important function in the fields of biosensors, supercapacitors, flexible wearable electronics, and the like.
However, the chitosan-based hydrogel has poor mechanical properties, and the mechanical strength and toughness still have certain limitations, which greatly limits the application of the chitosan-based hydrogel in various fields. Therefore, it is important to improve the mechanical properties. In addition, the gel mechanical property is further designed and optimized, so that the gel has special functions of bionic mechanical property, super elasticity, shape memory, high expansion performance and the like, and is an important development direction of the gel.
Disclosure of Invention
The invention aims to optimize the preparation method of the conventional chitosan cryogel, further improve the mechanical property of the cryogel and provide the shape memory chitosan hydrogel and the preparation method thereof.
According to the invention, the preparation method of the shape memory chitosan hydrogel is provided, which comprises the following steps: dissolving chitosan under acidic condition to obtain chitosan solution, adding alkali liquor under high-speed shearing condition, deprotonating chitosan under alkaline condition, converting the solution to gel direction, and under the action of strong shearing force, making chitosan molecular chain undergo the process of primary assembly so as to obtain the chitosan fibre bundle suspension (diameter is about 50 nm, length is about several micrometers) (figure 1) with good stability. Adding a cross-linking agent, stirring and mixing uniformly, concentrating to obtain cross-linked concentrated chitosan fiber bundle suspension liquid with different concentrations, and placing the suspension liquid into a mould with a required shape. Placing for a period of time to enable the chitosan and the cross-linking agent to fully react, then placing in a low-temperature environment for secondary assembly, wherein the growth of ice crystals promotes the concentration of the chitosan and the cross-linking agent in the microphase, promotes the cross-linking reaction, and further forms tough gel. And then unfreezing, so that the water-triggered shape memory chitosan hydrogel can be obtained.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of shape memory chitosan hydrogel is characterized by comprising the following steps:
preparing a chitosan solution in step (1): dissolving chitosan under acidic conditions to obtain a chitosan solution;
step (2) preparing a chitosan fiber bundle suspension with good stability: stirring the chitosan solution in the step (1) at a high speed by using a homogenizer, and simultaneously dropwise adding an alkaline solution with a certain volume; stirring for a period of time to obtain a stable chitosan fiber bundle suspension;
step (3) concentrating the chitosan fiber bundle suspension obtained in the step (2) to obtain concentrated suspension, injecting the concentrated suspension into a mold with a required shape, and standing for a period of time to enable the chitosan and the cross-linking agent to fully react;
step (4) placing the mold placed in the step (3) in a refrigerator for freezing for a certain time to obtain a frozen body;
and (5) unfreezing the frozen body obtained in the step (4) to obtain the chitosan hydrogel with the shape memory function, namely the shape memory chitosan hydrogel.
Preferably, in the step (1), the chitosan solution has a mass fraction of chitosan of 0.2-4%.
Preferably, in the step (2), the homogenizer is stirred at a high speed of 2000 to 18000 rpm.
Preferably, in the step (2), the stirring time is 3-30 min.
Preferably, in the step (2), the alkaline solution is NaOH or K (OH)2、Na2CO3、NaHCO3Any one or more of them.
Preferably, in the step (2), the pH of the suspension reaches 7-14 after the alkaline solution is added.
Preferably, in the step (3), before the suspension is concentrated, a crosslinking agent is added to the chitosan fiber bundle suspension to obtain a crosslinked chitosan fiber bundle suspension, and then the crosslinked chitosan fiber bundle suspension is concentrated to obtain a concentrated suspension.
Preferably, in the step (3), the cross-linking agent is any one or a combination of more of glutaraldehyde, vanillin, formaldehyde, terephthalaldehyde, epichlorohydrin, genipin and the like, and the mass ratio of the cross-linking agent to chitosan is 0.001-3: 1.
Preferably, in the step (3), the concentration method includes forced concentration by using a centrifuge, a rotary evaporator, a suction filter, a filtering device, and the like, and natural evaporation concentration.
Preferably, in the step (3), the concentration method is centrifugal concentration by a centrifuge, the centrifugal speed is 500-10000 rpm, and centrifugally concentrated suspension can be obtained by skimming a supernatant after centrifugation.
Preferably, in step (3), the suspension after concentration has a solids content of 0.4 to 5%.
Preferably, in the step (3), the temperature range of the crosslinking is 0-80 ℃, and the time is 0-24 hours.
Preferably, in the step (4), the freezing temperature is less than 0 ℃, and the freezing time is prolonged by 0-24 hours on the basis of freezing the suspension.
Preferably, in the step (5), the thawing is performed naturally at room temperature.
The invention also provides shape memory chitosan hydrogel prepared by any one of the preparation methods.
Compared with the prior art, the invention has the following beneficial effects:
(1) the process from chitosan solution to gel is a step assembly process, firstly stirring at high speed and adding alkali to form fiber bundles, carrying out primary assembly, then carrying out primary concentration on suspension, then carrying out ice crystal growth extrusion under the condition of low temperature, further concentrating materials and carrying out a crosslinking reaction to carry out secondary assembly. The primary assembly to form the chitosan nano fiber bundle is one of the key links for improving the mechanical strength and elasticity of the gel, and is an improvement and optimization of the existing freezing gel method. Compared with the traditional freezing and gelling process starting from a solution state, the invention takes the fiber bundle as an initial state and provides a new idea for the freezing and gelling of the organic polymer.
(2) The chitosan gel with the communicated macroporous structure prepared by the method has excellent water absorption (the water absorption is 15-40 times). The chemical crosslinking improves the disadvantage that chitosan is not acid resistant and improves the mechanical properties of the gel. The hydrogel in the invention has the advantages of super elasticity (figure 3), cyclic compression fatigue resistance (the plastic deformation is less than 10 percent after 2000 cycles of compression in the aqueous phase) (figure 4), high plasticity and shape memory (the shape can be basically recovered after the hydrogel is placed in water for 3s after compression and dehydration) (figure 5).
(3) The chitosan gel can be obtained by one-time freezing-unfreezing, the freezing and concentration process of ice crystal growth exists, the usage amount of the cross-linking agent is reduced, and the preparation process is very simple; the preparation period is short, and large-scale preparation is very easy to realize. Provides a foundation for obtaining the chitosan aerogel with simple preparation process and greatly reduced cost.
Drawings
Fig. 1 is a transmission electron microscope image of a chitosan fiber bundle obtained in step (2) of the embodiment of the present invention, wherein fig. 1 (a), fig. 1 (b), and fig. 1 (c) are high-magnification transmission electron microscope images of the chitosan fiber bundle obtained by low-speed, medium-speed, and high-speed stirring, respectively, and fig. 1 (d), fig. 1 (e), and fig. 1 (f) are low-magnification transmission electron microscope images of the chitosan fiber bundle obtained by low-speed, medium-speed, and high-speed stirring, respectively.
FIG. 2 is a scanning electron micrograph of the prepared chitosan hydrogel.
FIG. 3 is a graph of the compressive stress-strain of the shape-memory chitosan hydrogel prepared in example 1 in the aqueous phase.
FIG. 4 is a stress-strain diagram of the shape-memory chitosan hydrogel prepared in example 1 compressed 2000 times in water phase cycles.
Fig. 5 is a photograph of the shape-memory chitosan hydrogel prepared in example 1, which fixed and restored the shape.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
(1) Adding 0.2g of chitosan into a beaker filled with 99.8g of deionized water, dropwise adding 0.2ml of glacial acetic acid in the magnetic stirring process, and continuously stirring for 2 hours to obtain a chitosan solution;
(2) preparing chitosan fiber bundle suspension with good stability. Stirring the chitosan solution in step (1) at 2000rpm using a homogenizer while adding a volume of Na dropwise2CO3The solution (0.5mol/L) was brought to pH 7; stirring for 5min to obtain stable white milky chitosan fiber bundle suspension;
(3) adding glutaraldehyde with the concentration of 20% (the mass ratio of the glutaraldehyde to the chitosan is 1: 1) into the white milky chitosan fiber bundle suspension liquid obtained in the step (2), and uniformly mixing to obtain a cross-linked chitosan fiber bundle suspension liquid;
(4) centrifuging and concentrating the suspension obtained in the step (3) by a centrifuge at the rotating speed of 500rpm, removing supernatant to obtain concentrated crosslinked chitosan fiber bundle suspension, injecting the concentrated crosslinked chitosan fiber bundle suspension into a 12-hole polytetrafluoroethylene plate mould, wherein the shape of each hole of the mould is the shape of the required hydrogel, the adding amount of each hole is 5ml, and the mould is placed at 4 ℃ for 8 hours for a period of time;
(5) placing the 12-hole polytetrafluoroethylene plate mold injected with the suspension in a refrigerator at the temperature of-10 ℃ for freezing for 12h to obtain a frozen body;
(6) and (5) unfreezing the frozen body obtained in the step (5) at room temperature to obtain the shape memory chitosan hydrogel.
Example 2
(1) Adding 4g of chitosan into a beaker filled with 96g of deionized water, dropwise adding 1.5ml of concentrated hydrochloric acid in the magnetic stirring process, and continuously stirring for 16 hours to obtain a chitosan solution;
(2) preparing chitosan fiber bundle suspension with good stability. Stirring the chitosan solution of step (1) using a homogenizer at 18000rpm while dropping a certain volume of K (OH)2The solution (0.5mol/L) was brought to pH 12; stirring for 6min to obtain stable white milky chitosan fiber bundle suspension;
(3) and (3) centrifugally concentrating the white milky chitosan fiber bundle suspension obtained in the step (2) by a centrifugal machine at the rotating speed of 10000rpm, removing the supernatant to obtain concentrated chitosan fiber bundle suspension, injecting the concentrated chitosan fiber bundle suspension into a 6-hole polytetrafluoroethylene plate mould, wherein the shape of each hole of the mould is the shape of the hydrogel to be prepared, and the adding amount of each hole is 6 ml.
(4) Placing the 6-hole polytetrafluoroethylene plate mould injected with the suspension in a refrigerator at-80 ℃ for freezing for 1h to obtain a frozen body;
(5) and (4) unfreezing the frozen body obtained in the step (4) at room temperature to obtain the shape memory chitosan hydrogel.
Example 3
Adding 1g of chitosan into a beaker filled with 99g of deionized water, dropwise adding 0.45ml of glacial acetic acid in the magnetic stirring process, and continuously stirring for 4 hours to obtain a chitosan solution;
(2) preparing chitosan fiber bundle suspension with good stability. Stirring the chitosan solution in the step (1) by using a homogenizer at the speed of 5000rpm, and simultaneously dropwise adding a certain volume of NaOH solution (1mol/L) to enable the pH value to reach 14; stirring for 8min to obtain stable white milky chitosan fiber bundle suspension;
(3) adding epoxy chloropropane (the mass ratio of epoxy chloropropane to chitosan is 3: 1) into the white milky chitosan fiber bundle suspension liquid obtained in the step (2), and uniformly mixing to obtain a crosslinked chitosan fiber bundle suspension liquid;
(4) centrifuging and concentrating the crosslinked chitosan fiber bundle suspension obtained in the step (3) by a centrifuge at the rotating speed of 3000rpm, removing supernatant fluid to obtain concentrated crosslinked chitosan fiber bundle suspension, injecting the concentrated crosslinked chitosan fiber bundle suspension into a silica gel mold, and standing for 8 hours at the temperature of 80 ℃ for a period of time;
(5) placing the silica gel mold injected with the suspension in a refrigerator at-20 ℃ for freezing for 12h to obtain a frozen body;
(6) and (5) unfreezing the frozen body obtained in the step (5) at room temperature to obtain the shape memory chitosan hydrogel.
Example 4
(1) Adding 2g of chitosan into a beaker filled with 98g of deionized water, dropwise adding 0.85ml of glacial acetic acid in the magnetic stirring process, and continuously stirring for 6 hours to obtain a chitosan solution;
(2) preparing chitosan fiber bundle suspension with good stability. Stirring the chitosan solution in the step (1) by using a homogenizer at a speed of 8000rpm, and simultaneously dropwise adding a certain volume of NaOH (1mol/L) solution to enable the pH value to reach 8; stirring for 10min to obtain stable white milky chitosan fiber bundle suspension;
(3) adding phthalaldehyde (the mass ratio of the phthalaldehyde to the chitosan is 0.5: 1) into the suspension liquid obtained in the step (2), and uniformly mixing to obtain a crosslinked chitosan fiber bundle suspension liquid;
(4) treating the crosslinked chitosan fiber bundle suspension obtained in the step (3) for 2 hours (at the temperature of 30 ℃) by using a rotary evaporator, removing supernatant liquid to obtain concentrated crosslinked chitosan fiber bundle suspension, injecting the concentrated crosslinked chitosan fiber bundle suspension into an organic glass container, and standing for 24 hours at the temperature of 25 ℃ for a period of time;
(5) placing the machine glass container injected with the suspension in a refrigerator at the temperature of-10 ℃ for freezing for 24 hours to obtain a frozen body;
(6) and (5) unfreezing the frozen body obtained in the step (5) at room temperature to obtain the shape memory chitosan hydrogel.
Example 5
(1) Adding 3g of chitosan into a beaker filled with 97g of deionized water, dropwise adding 1.25ml of concentrated hydrochloric acid in the magnetic stirring process, and continuously stirring for 12 hours to obtain a chitosan solution;
(2) preparing chitosan fiber bundle suspension with good stability. Stirring the chitosan solution in the step (1) by using a homogenizer at 13000rpm, and simultaneously dropwise adding a certain volume of NaHCO3The solution (0.5mol/L) was brought to pH 7; stirring for 15min to obtain a stable white milky chitosan fiber bundle suspension;
(3) adding genipin (the mass ratio of genipin to chitosan is 0.001: 1) into the suspension liquid obtained in the step (2), and uniformly mixing to obtain a crosslinked chitosan fiber bundle suspension liquid;
(4) concentrating the crosslinked chitosan fiber bundle suspension obtained in the step (3) by using a suction filter for 10 minutes (medium-speed qualitative filter paper), removing supernatant to obtain concentrated crosslinked chitosan fiber bundle suspension, injecting the concentrated crosslinked chitosan fiber bundle suspension into a glass container, and standing for 1 hour at 20 ℃;
(5) placing the glass container into which the suspension is injected into a refrigerator at the temperature of-20 ℃ for freezing for 12 hours to obtain a frozen body;
(6) and (5) unfreezing the frozen body obtained in the step (5) at room temperature to obtain the shape memory chitosan hydrogel.
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 (6)
1. The preparation method of the shape memory chitosan hydrogel is characterized by comprising the following steps:
preparing a chitosan solution in step (1): dissolving chitosan under acidic conditions to obtain a chitosan solution;
step (2) preparing a chitosan fiber bundle suspension with good stability: stirring the chitosan solution in the step (1) at a high speed by using a homogenizer, and simultaneously dropwise adding an alkaline solution with a certain volume; stirring for a period of time to obtain a stable chitosan fiber bundle suspension;
step (3) concentrating the chitosan fiber bundle suspension obtained in the step (2) to obtain concentrated suspension, injecting the concentrated suspension into a mold with a required shape, and standing for a period of time to enable the chitosan and the cross-linking agent to fully react;
step (4) placing the mold placed in the step (3) in a refrigerator for freezing for a certain time to obtain a frozen body;
step (5) unfreezing the frozen body obtained in the step (4) to obtain the chitosan hydrogel with the shape memory function, namely the shape memory chitosan hydrogel;
in the step (1), the mass fraction of chitosan in the polysaccharide solution is 0.2-4%;
in the step (2), the high-speed stirring speed of the homogenizer is 2000-18000 rpm; adding an alkaline solution to enable the pH of the suspension to reach 7-14;
in the step (3), before the suspension is concentrated, adding a cross-linking agent into the chitosan fiber bundle suspension to obtain a cross-linked chitosan fiber bundle suspension, and then concentrating the cross-linked chitosan fiber bundle suspension to obtain a concentrated suspension, wherein the cross-linking agent is any one or a combination of more of glutaraldehyde, vanillin, formaldehyde, terephthalaldehyde, epichlorohydrin and genipin, and the mass ratio of the cross-linking agent to chitosan is 0.001-3: 1; the temperature range of the placing and crosslinking is 0-80 ℃, and the time is 0-24 h.
2. The method for preparing a shape-memory chitosan hydrogel according to claim 1, wherein: in the step (2), the alkaline solution is NaOH or K (OH)2、Na2CO3、NaHCO3Any one or more of them.
3. The method for preparing a shape-memory chitosan hydrogel according to claim 1, wherein: in the step (3), the concentration method comprises forced concentration by using a centrifuge, a rotary evaporator, a suction filter and a filtering device, and natural evaporation concentration.
4. The method for preparing a shape-memory chitosan hydrogel according to claim 1, wherein: in the step (3), the concentration method is to adopt a centrifugal machine for centrifugal concentration, the centrifugal speed is 500-10000 rpm, and after centrifugation, supernatant liquid is skimmed to obtain centrifugally concentrated suspension liquid.
5. The method for preparing a shape-memory chitosan hydrogel according to claim 1, wherein: in the step (4), the freezing temperature is less than 0 ℃, and the freezing time is prolonged by 0-24 hours on the basis of freezing the suspension.
6. A shape memory chitosan hydrogel, which is characterized in that: prepared by the preparation method of any one of claims 1 to 5.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820352A (en) * | 2016-04-06 | 2016-08-03 | 南京林业大学 | Method for preparing electropositive chitin nanofiber hydrogel and aerogel |
| CN106220867A (en) * | 2016-08-04 | 2016-12-14 | 南京林业大学 | A kind of elecrtonegativity chitin nanofiber hydrogels and the preparation method of aeroge |
| CN108341977A (en) * | 2018-03-13 | 2018-07-31 | 武汉理工大学 | A kind of citric acid cross-linked chitosan hydrogel and preparation method thereof |
| CN109265758A (en) * | 2018-09-12 | 2019-01-25 | 南京林业大学 | A kind of bis- response type chitin nanofiber hydrogels of temperature/pH and preparation method thereof |
| CN109999221A (en) * | 2019-04-12 | 2019-07-12 | 清华大学 | A kind of orientation chitin fiber hydrogel and preparation method thereof |
| CN110982125A (en) * | 2019-12-19 | 2020-04-10 | 武汉纺织大学 | Shape self-recovery porous composite gel and preparation method and application thereof |
| CN111171384A (en) * | 2020-02-10 | 2020-05-19 | 东华大学 | Light warm-keeping flexible chitosan/nano-cellulose aerogel and preparation method thereof |
| CN111518305A (en) * | 2019-02-01 | 2020-08-11 | 武汉大学 | Preparation method of chitosan gel material |
| CN112316202A (en) * | 2020-11-13 | 2021-02-05 | 南通大学 | Shape memory hemostatic material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2780294C (en) * | 2009-11-09 | 2018-01-16 | Spotlight Technology Partners Llc | Polysaccharide based hydrogels |
-
2021
- 2021-02-03 CN CN202110152190.9A patent/CN112940287B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820352A (en) * | 2016-04-06 | 2016-08-03 | 南京林业大学 | Method for preparing electropositive chitin nanofiber hydrogel and aerogel |
| CN106220867A (en) * | 2016-08-04 | 2016-12-14 | 南京林业大学 | A kind of elecrtonegativity chitin nanofiber hydrogels and the preparation method of aeroge |
| CN108341977A (en) * | 2018-03-13 | 2018-07-31 | 武汉理工大学 | A kind of citric acid cross-linked chitosan hydrogel and preparation method thereof |
| CN109265758A (en) * | 2018-09-12 | 2019-01-25 | 南京林业大学 | A kind of bis- response type chitin nanofiber hydrogels of temperature/pH and preparation method thereof |
| CN111518305A (en) * | 2019-02-01 | 2020-08-11 | 武汉大学 | Preparation method of chitosan gel material |
| CN109999221A (en) * | 2019-04-12 | 2019-07-12 | 清华大学 | A kind of orientation chitin fiber hydrogel and preparation method thereof |
| CN110982125A (en) * | 2019-12-19 | 2020-04-10 | 武汉纺织大学 | Shape self-recovery porous composite gel and preparation method and application thereof |
| CN111171384A (en) * | 2020-02-10 | 2020-05-19 | 东华大学 | Light warm-keeping flexible chitosan/nano-cellulose aerogel and preparation method thereof |
| CN112316202A (en) * | 2020-11-13 | 2021-02-05 | 南通大学 | Shape memory hemostatic material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Chitosan scaffolds with a shape memory effect induced by hydration;Cristina O. Correia等;《Journal of Materials Chemistry B》;20140321;第2卷;第3315-3323页 * |
| 不同酸制备的几丁质纳米纤维凝胶材料;王蓉等;《第二届气凝胶材料国际学术研讨会论文集》;20171101;第151-156页 * |
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