CN112852002A - Preparation method of super-elastic halloysite-chitosan composite aerogel - Google Patents
Preparation method of super-elastic halloysite-chitosan composite aerogel Download PDFInfo
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- CN112852002A CN112852002A CN202110214647.4A CN202110214647A CN112852002A CN 112852002 A CN112852002 A CN 112852002A CN 202110214647 A CN202110214647 A CN 202110214647A CN 112852002 A CN112852002 A CN 112852002A
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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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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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
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
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Abstract
The invention discloses a preparation method of a super-elastic halloysite-chitosan composite aerogel, which comprises the following steps: adding halloysite into a certain amount of chitosan acetic acid solution, and ultrasonically stirring to prepare a well-dispersed halloysite/chitosan dispersion liquid; pouring the well-dispersed halloysite/chitosan dispersion into a polytetrafluoroethylene mold, freezing by using a two-way freezing method, and then putting into a freeze dryer for drying for 24 hours to obtain the halloysite-chitosan composite aerogel. The preparation method is simple in condition and environment-friendly, and the prepared composite aerogel has superelasticity and has great potential application value in the aspects of fire prevention, heat preservation, supercapacitors, battery electrodes and the like.
Description
Technical Field
The invention relates to the field of material science, in particular to a preparation method of a super-elastic halloysite-chitosan composite aerogel.
Background
Aerogel is a light material with network structure and nano-porosity, which is formed by the mutual accumulation of high polymer molecules or colloidal particles, and is the lowest density among the solid materials known in the world at present. Because the aerogel has high porosity, high specific surface area and very low thermal conductivity, the aerogel has good research prospects when being applied to various aspects, such as fire protection, construction, packaging, environmental protection, aerospace and the like.
Halloysite is a natural nanotubular clay mineral encapsulated in an aluminosilicate layered structure obtained by the 1:1 co-oxygen linkage of silicon-oxygen tetrahedrons and aluminum-oxygen octahedrons. The chemical difference between the inner and outer surfaces of the halloysite results in a positive zeta potential on the inner surface of the hollow tube and a negative zeta potential on the outer surface of the halloysite in an environment having a pH in the range of 2.5 to 8.5. The halloysite nanotube has a special structure, excellent mechanical properties and biocompatibility, low cost, natural formation, no toxicity, no harm, good biocompatibility and active hydroxyl groups on the surface and between layers, so that the halloysite nanotube has many potential important applications in different fields. Halloysite is used as a raw material and is compounded with a high polymer material to prepare the halloysite-based high polymer aerogel, which is paid attention by some researchers in recent years. Currently, the research content mainly focuses on the preparation of composite aerogel by mixing halloysite and polyvinyl alcohol or other high molecular materials. However, the aerogel prepared by using the mineral material as the substrate often has the problems of large brittleness, large hardness, non-compressibility and the like, and the practical application of the aerogel is severely limited, so that more research work is put on how to improve the strength of the mineral material-based composite aerogel, but the research effect is very small. Therefore, there is a need to develop a halloysite/chitosan composite aerogel having superelasticity to solve the above problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of superelastic halloysite-chitosan composite aerogel, which mainly takes halloysite as a substrate, mixes the halloysite and chitosan through electrostatic interaction, and obtains the halloysite-chitosan composite aerogel with superelasticity through a two-way freezing method. The preparation method is simple in condition and environment-friendly, and the prepared composite aerogel has superelasticity and has great potential application value in the aspects of fire prevention, heat preservation, supercapacitors, battery electrodes and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a preparation method of superelastic halloysite-chitosan composite aerogel, which comprises the steps of adding halloysite into a certain amount of chitosan acetic acid solution, and ultrasonically stirring to prepare a well-dispersed halloysite/chitosan dispersion liquid; pouring the well-dispersed halloysite/chitosan dispersion into a polytetrafluoroethylene mold, freezing by using a two-way freezing method, and drying in a freeze dryer to obtain the halloysite-chitosan composite aerogel.
Specifically, the method comprises the following steps:
1) preparing a chitosan acetic acid solution: adding chitosan powder into 4% acetic acid solution as solvent, and ultrasonically stirring to prepare 40mg/mL chitosan acetic acid solution;
2) adding distilled water into the solution obtained in the step 1) to dilute the solution until the concentration is 16-40 mg/mL, adding a certain amount of halloysite, and performing ultrasonic dispersion for 30 minutes to obtain a halloysite-chitosan dispersion liquid with uniform dispersion. The mass ratio of the chitosan to the halloysite is 1 (1-5), preferably 1: (2-3).
3) Pouring the dispersion liquid obtained in the step 2) into a polytetrafluoroethylene mold, and freezing the sample by adopting a bidirectional freezing method.
4) And (3) drying the frozen sample obtained in the step 3) in a freeze dryer for 24 hours to obtain the super-elastic halloysite-chitosan composite aerogel.
According to the invention, halloysite is used as a substrate, and is mixed with chitosan through electrostatic interaction, and then the halloysite-chitosan composite aerogel with super elasticity is obtained through a two-way freezing method. The preparation method is simple in condition and environment-friendly, and the prepared composite aerogel has superelasticity and has great potential application value in the aspects of fire prevention, heat preservation, supercapacitors, battery electrodes and the like.
Compared with other prior art, the invention has the following advantages:
1) according to the invention, halloysite and chitosan are compounded to synthesize the halloysite-chitosan composite aerogel with super elasticity for the first time.
2) The preparation method disclosed by the invention is simple in preparation conditions, green and environment-friendly in raw materials, and lower in cost compared with other hyperelastic aerogels such as graphene and carbon nanotubes.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
Fig. 2 is a picture of a real object of the halloysite-chitosan composite aerogel prepared by the invention.
Fig. 3 is a scanning electron microscope picture of the halloysite-chitosan composite aerogel prepared by the invention.
Fig. 4 is a fatigue test result of 10 compression rebounds of the halloysite-chitosan composite aerogel prepared in the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
Example 1
1) Adding chitosan powder into 4% acetic acid solution as solvent, and ultrasonically stirring to prepare 40mg/mL chitosan acetic acid solution;
2) taking 12 mL of the solution obtained in the step 1), adding distilled water to dilute the solution to 15 mL. Adding 480 mg of halloysite into the solution, and performing ultrasonic dispersion for 30 minutes to obtain a halloysite-chitosan dispersion liquid with uniform dispersion.
3) Pouring the dispersion liquid obtained in the step 2) into a mould, and carrying out bidirectional freezing on the sample by adopting a bidirectional freezing method.
4) And (3) drying the frozen sample obtained in the step 3) in a freeze dryer for 24 hours to obtain the super-elastic halloysite-chitosan composite aerogel.
Example 2
This example is different from example 1 in that 6 mL of the chitosan solution obtained in step 1) was taken in step 2, and 720 mg of halloysite was added to the solution, but the other examples were the same as example 1.
Example 3
This example is different from example 1 in that 8 mL of the chitosan solution obtained in step 1) was taken in step 2, and 640 mg of halloysite was added to the solution, but the other examples were the same as example 1.
Example 4
This embodiment is different from example 1 in that 15 mL of the chitosan solution obtained in step 1) was taken in step 2, and 0mg of halloysite was added to the solution, but the other steps were the same as example 1.
FIG. 1 is a schematic diagram of the preparation process of the present invention, in which a halloysite-chitosan solution is first frozen in two directions to form layered ice crystals, and then is dried by freeze-drying to form layered aerogel.
Fig. 2 is a real object diagram of the halloysite-chitosan composite aerogel prepared by the invention, which is a block solid.
FIG. 3 is a scanning electron microscope image of the halloysite-chitosan composite aerogel prepared by the invention, wherein the microstructure is a lamellar structure, the thickness of a lamellar layer is 1-5 microns, and the gap of the lamellar layer is 20-50 microns.
Fig. 4 is a stress-strain diagram of 10 compression rebounds of the halloysite-chitosan composite aerogel prepared in the invention. From the figure, it can be found that the halloysite-chitosan composite aerogel still maintains better compression resilience characteristics after 10 times of compression resilience, has small structural damage and shows super elasticity.
According to the method, the halloysite is used as a substrate, the halloysite and chitosan are mixed through electrostatic interaction, and then the halloysite-chitosan composite aerogel can be obtained through a two-way freezing method. The preparation method is simple in condition and environment-friendly, and the prepared composite aerogel has superelasticity and has great potential application value in the aspects of fire prevention, heat preservation, supercapacitors, battery electrodes and the like.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (4)
1. The preparation method of the superelastic halloysite-chitosan composite aerogel is characterized in that the halloysite and the chitosan are compounded, so that the composite material has superelasticity.
2. The method for preparing a superelastic halloysite-chitosan composite aerogel according to claim 1, wherein the aerogel is obtained by performing bidirectional freezing on a mixed solution of chitosan and halloysite.
3. The method for preparing the superelastic halloysite-chitosan composite aerogel according to claim 1 or 2, comprising the steps of:
1) preparing a chitosan acetic acid solution: adding chitosan powder into 4% acetic acid solution as solvent, and ultrasonically stirring to prepare 40mg/mL chitosan acetic acid solution;
2) adding distilled water into the solution obtained in the step 1) to dilute the solution until the concentration is 16-40 mg/mL, adding a certain amount of halloysite, and performing ultrasonic dispersion for 30 minutes to obtain a uniformly dispersed halloysite-chitosan dispersion liquid; the mass ratio of the chitosan to the halloysite is 1 (1-5);
3) pouring the dispersion liquid obtained in the step 2) into a polytetrafluoroethylene mold, and freezing the sample by adopting a bidirectional freezing method.
4) And (3) drying the frozen sample obtained in the step 3) in a freeze dryer for 24 hours to obtain the super-elastic halloysite-chitosan composite aerogel.
4. The method for preparing the superelastic halloysite-chitosan composite aerogel according to claim 3, wherein in the step 2), the mass ratio of the chitosan to the halloysite is 1: (2-3).
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| CN202110214647.4A CN112852002A (en) | 2021-02-26 | 2021-02-26 | Preparation method of super-elastic halloysite-chitosan composite aerogel |
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| CN202110214647.4A CN112852002A (en) | 2021-02-26 | 2021-02-26 | Preparation method of super-elastic halloysite-chitosan composite aerogel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480847A (en) * | 2021-07-22 | 2021-10-08 | 广东石油化工学院 | Preparation method of composite board with strong mechanical property and energy storage characteristic |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113480847A (en) * | 2021-07-22 | 2021-10-08 | 广东石油化工学院 | Preparation method of composite board with strong mechanical property and energy storage characteristic |
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