CN111100291A - Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam - Google Patents
Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam Download PDFInfo
- Publication number
- CN111100291A CN111100291A CN201811250877.0A CN201811250877A CN111100291A CN 111100291 A CN111100291 A CN 111100291A CN 201811250877 A CN201811250877 A CN 201811250877A CN 111100291 A CN111100291 A CN 111100291A
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- polybenzoxazine
- dimensional graphene
- preparation
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
- 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
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
- C08J9/008—Nanoparticles
-
- 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
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to a preparation method of polybenzoxazine reinforced three-dimensional graphene foam, which comprises the following steps: dripping an organic solution containing a benzoxazine monomer into a graphene oxide aqueous solution and uniformly mixing to obtain a mixed solution; carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 80-210 ℃ for 6-48 hours, and then washing and drying to obtain the polybenzoxazine enhanced three-dimensional graphene foam.
Description
Technical Field
The invention relates to a preparation method of polybenzoxazine reinforced three-dimensional graphene foam, and belongs to the field of preparation of three-dimensional graphene.
Background
The graphene aerogel is a three-dimensional porous material constructed by graphene nano, has the characteristics of low density, high conductivity, high specific surface area, high porosity and the like, and has great application prospects in the fields of energy, environment, electronics and the like. So far, methods for preparing three-dimensional graphene macroscopic blocks mainly include a chemical self-assembly method, a chemical vapor deposition method, a template method, and the like. Such as: a method for preparing three-dimensional graphene by combining a template method and a CVD method is reported in (chinese publication No. CN105523546A), however, the method needs to remove a metal template, so that the preparation cost is greatly increased. Meanwhile, the CVD method has higher temperature and larger energy consumption in the preparation process, and is not beneficial to large-scale production. Patent (chinese publication No. CN103910356A) reports a method for synthesizing a three-dimensional graphene block by hydrothermal method using carbonate as a template, and although the formation of a uniform pore structure inside the three-dimensional graphene can be controlled by using carbonate as a template, the three-dimensional graphene prepared by the method has poor mechanical properties, and cannot be widely applied.
Most of the reported three-dimensional graphene aerogels are brittle structures due to high porosity, and have poor mechanical strength. When subjected to compressive stress, plastic deformation or brittle fracture tends to occur, resulting in structural failure, which greatly limits its further widespread use. Therefore, research and development of a porous three-dimensional graphene structure with high mechanical strength and high elasticity are important directions for graphene research.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for preparing a polybenzoxazine reinforced three-dimensional graphene foam, including:
dripping an organic solution containing a benzoxazine monomer into a graphene oxide aqueous solution and uniformly mixing to obtain a mixed solution; carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 80-210 ℃ for 6-48 hours, and then washing and drying to obtain the polybenzoxazine enhanced three-dimensional graphene foam.
According to the invention, polybenzoxazine and graphene are combined to prepare the aerogel. Specifically, a benzoxazine monomer is polymerized into a thermosetting polymer (crosslinked network) in a hydrothermal process to fully crosslink a graphene nanosheet layer, so that the rapid and high-quality preparation of the three-dimensional graphene foam is realized, wherein the graphene nanosheet layer has high strength and high elasticity (the hydrogel has better elasticity after hydrothermal treatment, as shown in figure 2, the hydrogel can be completely recovered after compression, and finally the aerogel after heat treatment has better mechanical strength and can bear a heavy object 600 times of the weight of the aerogel without damaging the structure). The long-chain structure of the polybenzoxazine polymer can adjust the change of conformation through the movement of a molecular chain when the polybenzoxazine polymer is acted by an external force so as to adapt to the action of the external force, so that the polybenzoxazine polymer has better elasticity under specific conditions. The polybenzoxazine polymer is introduced into a three-dimensional graphene system, so that the function of crosslinking graphene sheets can be achieved, stress can be dispersed and transferred, and the construction of a high-strength three-dimensional graphene structure is realized.
Preferably, the concentration of the graphene oxide aqueous solution is 1mg/ml to 15 mg/ml; preferably, the graphene oxide is prepared by adopting a modified Hummers method.
Preferably, the mass concentration of the benzoxazine monomer in the organic solution containing the benzoxazine monomer is 0.4-30%, and preferably 0.5-30%.
Preferably, the benzoxazine monomer is selected from at least one of 3, 4-dihydro-1, 3 benzoxazine, bisphenol a type benzoxazine, diphenylmethane diamine type benzoxazine, polycyclic benzoxazine and diallyl dibenzooxazine.
Preferably, the benzoxazine monomer accounts for 0.5-60% of the mass of the graphene oxide. When the amount of benzoxazine is too small, the improvement of mechanical strength is limited, and when the amount of benzoxazine is too large, the material becomes brittle.
Preferably, the organic solvent in the organic solution containing benzoxazine monomer is at least one of acetone, diethyl ether, dimethylformamide, dimethyl sulfoxide, toluene, xylene, dichloromethane and chloroform.
Preferably, the dropping rate is 0.5-5 ml/min. The purpose of slow dropwise adding is to enable an organic solution of benzoxazine to be more fully and uniformly mixed with a graphene oxide aqueous solution to form a similar oil-in-water structure, and organic molecules are attached to a two-phase interface to achieve an enhancement effect more easily. The too fast local concentration that can lead to of dropwise add speed is too big, and the benzoxazine monomer mixes inhomogeneously with oxidation graphite alkene, can arouse the defect of aerogel inside, and intensity reduces.
Preferably, the drying mode is one of freeze drying, vacuum drying and supercritical drying.
On the other hand, the invention also provides a three-dimensional graphene aerogel, which is obtained by annealing the polybenzoxazine reinforced three-dimensional graphene foam prepared by the preparation method at the temperature of 200-1000 ℃.
Has the advantages that:
in the invention, no micromolecule is released in the forming and curing process of the selected polybenzoxazine, the porosity of the product is low and is close to zero shrinkage, so that the polybenzoxazine has the characteristics of high modulus, high strength, good heat resistance, low water absorption and the like. The specific reinforcement thereof is caused by the crosslinked structure existing in a large amount in the internal structure. It should be understood that the enhancement of the present invention refers to the enhancement of lower density (8-30 mg/cm)3) The strength of the aerogel of (a), and the aerogel density is extremely low. At the same time, the aerogel of the invention also has a high specific surface area (600 m) after being reheated (action of residual catalyst)2/g), higher conductivity and stronger adsorption performance. In addition, relative to comparative example 1, the addition amount of the benzoxazine is 0.5-15% of the mass of GO;
in the invention, the preparation of the three-dimensional graphene aerogel with high mechanical strength can be realized by only adopting a simple hydrothermal method, and the polymerization degree of the benzoxazine can be adjusted by adjusting the type and concentration of the added benzoxazine, the reaction time and the reaction temperature, so that the mechanical strength of the synthesized three-dimensional graphene is controlled, and the conversion from high-elasticity to high-hardness materials is realized. Meanwhile, the preparation method is simple and feasible, and can realize the macro preparation of the three-dimensional graphene. The three-dimensional graphene prepared by the method has smaller density, larger specific surface area and higher conductivity, and has great application prospects in the fields of catalysis, energy, environment, adsorption and the like.
Drawings
Fig. 1 is a hydrogel of benzoxazine-reinforced three-dimensional graphene prepared in example 3, from which it can be seen that the polybenzoxazine-reinforced three-dimensional graphene hydrogel has an intact structure and few defects, and fig. 2 is a compression performance test thereof;
FIG. 2 is a test of elasticity of the hydrogel prepared in example 3, wherein (a) before compression, (b) after compression, (c) after compression;
fig. 3 is the three-dimensional graphene aerogel after annealing treatment in example 3, and it can be seen from the figure that the three-dimensional graphene structure is maintained relatively intact after annealing treatment;
fig. 4 is a scanning electron microscope picture of the three-dimensional graphene aerogel in example 3, from which it can be seen that the three-dimensional graphene aerogel has a porous structure composed of graphene nanosheets;
fig. 5 is a macroscopic view of the reinforced three-dimensional graphene in example 3 (placed on a plastic glove, the glove is not deformed);
fig. 6 is a graph of the reinforced three-dimensional graphene in example 3 (bearing 600 times of weight, the three-dimensional graphene structure still exists stably).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the benzoxazine monomer is first dissolved in an organic solvent and then slowly added to the dispersion of graphene oxide. And then, in the hydrothermal process, a benzoxazine monomer is polymerized to form a thermosetting polymer, and the graphene sheet layer can be crosslinked, so that the mechanical strength of the three-dimensional graphene foam is greatly improved, and meanwhile, a certain pore-forming effect is achieved by adding an organic solvent. The preparation method is simple and feasible, and can realize large-scale production.
The following exemplarily illustrates a preparation method of a polybenzoxazine-reinforced three-dimensional graphene foam.
And ultrasonically dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution. Wherein the ultrasonic time can be 0.5-4 hours. The concentration of the graphene oxide aqueous solution is 1 mg/ml-15 mg/ml. Graphene oxide can be prepared by a modified Hummers method. It should be noted that other common methods in the art may also be used to prepare graphene oxide, such as the Brodietz method, Staudenmaier method, electrochemical exfoliation method, and the like.
Dissolving a certain amount of benzoxazine monomer in an organic solvent to obtain an organic solution containing the benzoxazine monomer. Wherein, the mass concentration of the benzoxazine monomer in the organic solution containing the benzoxazine monomer can be 0.4-30%, and is preferably 0.5-10%. Benzoxazine monomers include: 3, 4-dihydro-1, 3 benzoxazine, bisphenol A benzoxazine, diphenylmethane diamine benzoxazine, polycyclic benzoxazine and diallyl dibenzooxazine. The organic solvent can be one or more of acetone, diethyl ether, dimethylformamide, dimethyl sulfoxide, toluene, xylene, dichloromethane and chloroform.
Slowly and dropwise adding the organic solution containing the benzoxazine monomer into the graphene oxide dispersion liquid, and uniformly mixing to obtain a mixed solution. Wherein, the mixing mode can be ultrasonic treatment and/or stirring. The slow dripping rate can be 0.5-5 ml/min.
And transferring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at a certain temperature, and washing and drying to obtain the polybenzoxazine enhanced three-dimensional graphene foam. Wherein the hydrothermal reaction temperature can be 80-210 ℃, and the reaction time can be 6-48 hours. The drying may be one of freeze drying, vacuum drying, and supercritical drying.
As a preparation method of polybenzoxazine reinforced three-dimensional graphene foam, the method comprises the following steps:
(1) ultrasonically dispersing graphene oxide in deionized water to obtain a graphene oxide aqueous solution;
(2) and (2) dissolving a certain amount of benzoxazine monomer in an organic solvent, slowly dripping the benzoxazine monomer into the graphene oxide dispersion liquid obtained in the step (1), and carrying out ultrasonic treatment and stirring for a period of time (the ultrasonic stirring time is 0.5-8 h). After the solution is fully and uniformly mixed, transferring the solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction at a certain temperature;
(3) after reacting for a period of time, cooling the reaction kettle in the step (2) to room temperature, taking out the reacted hydrogel, and repeatedly washing the hydrogel by using deionized water and an organic solvent to remove unreacted benzoxazine monomers;
(4) and (4) freeze-drying the hydrogel in the step (3) to obtain the polybenzoxazine reinforced three-dimensional graphene foam.
And annealing the polybenzoxazine-enhanced three-dimensional graphene foam to obtain the three-dimensional graphene aerogel. Wherein the annealing temperature is 200-1000 deg.C, the annealing time is 1-4 hours, and the atmosphere is inert atmosphere (such as argon, nitrogen, etc.).
According to the invention, the density of the polybenzoxazine reinforced three-dimensional graphene aerogel subjected to annealing treatment is 8-60 mg/cm3(preferably 8 to 40 mg/cm)3) The specific surface area is 100-600 m measured by a nitrogen adsorption and desorption method or a specific surface area tester2And the electric conductivity is 10-80S/m measured by adopting a four-probe method (an electric conductivity tester), the compressive strength before annealing is 0.5-5 MPa measured by adopting an electronic universal tester, and the compressive strength after annealing is 0.2-MPa.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Firstly, graphene oxide was prepared by a modified Hummers method, a 4mg/ml graphene oxide aqueous solution (50ml) was prepared by means of ultrasonic and mechanical stirring, and then a 0.4% (mass concentration) acetone solution (2.5ml) of 3, 4-dihydro-1, 3 benzoxazine was slowly dropped (0.5 ml/min) into the graphene oxide dispersion, and after ultrasonic and stirring for 6 hours, the graphene oxide was transferred to a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at the temperature of 100 ℃ for 6 hours to obtain the polybenzoxazine enhanced graphene hydrogel. And washing and freeze-drying the hydrogel for 48 hours to obtain the polybenzoxazine reinforced three-dimensional graphene foam. Then placing the polybenzoxazine enhanced three-dimensional graphene foam into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon gas, carrying out annealing treatment for 3 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 17mg/cm3Specific surface area of 413m2(ii) a conductivity of 33S/m.
Example 2
Firstly, graphene oxide is prepared by adopting an improved Hummers method, 4mg/ml of graphene oxide aqueous solution (50ml) is prepared by means of ultrasound and mechanical stirring, then 2% of 3, 4-dihydro-1, 3 benzoxazine acetone solution/ml (2.5ml) and 2% of diphenylmethane diamine type benzoxazine toluene solution (2.5ml) are slowly dripped into the graphene oxide dispersion liquid in sequence (0.5 ml/min), and the graphene oxide dispersion liquid is transferred into a reaction kettle after being subjected to ultrasound and stirred for 6 hours. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 6 hours to obtain the thermosetting polybenzoxazine enhanced graphene hydrogel. And washing and freeze-drying the hydrogel for 48 hours to obtain the polybenzoxazine reinforced three-dimensional graphene foam. Then placing the polybenzoxazine enhanced three-dimensional graphene foam into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon gas, carrying out annealing treatment for 3 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 23mg/cm3A specific surface area of 384m2The electrical conductivity was 31S/m.
Example 3
Firstly, graphene oxide is prepared by a modified Hummers method, and is stirred by ultrasound and machineryA4 mg/ml graphene oxide aqueous solution (50ml) was prepared, and then 0.5ml of a DMF (N, N-dimethylformamide) solution of 8% diphenylmethane diamine benzoxazine was slowly added dropwise (0.5 ml/min) to the graphene oxide dispersion, subjected to ultrasonic treatment and stirred for 6 hours, and transferred to a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the thermosetting polybenzoxazine enhanced graphene hydrogel. And washing and freeze-drying the hydrogel for 48 hours to obtain the polybenzoxazine reinforced three-dimensional graphene foam. Then placing the polybenzoxazine enhanced three-dimensional graphene foam into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon gas, carrying out annealing treatment for 3 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 36mg/cm3Specific surface area of 473m2The specific conductivity was 50S/m.
Example 4
Firstly, preparing graphene oxide by adopting an improved Hummers method, preparing a 4mg/ml graphene oxide aqueous solution (50ml) by means of ultrasonic and mechanical stirring, sequentially dripping 2.5ml of a 2% acetone solution of 3, 4-dihydro-1, 3 benzoxazine and 2.5ml of a 2% (mass concentration) toluene solution of diphenylmethane diamine type benzoxazine (the dripping rates are respectively 1 ml/min and 1 ml/min) into the graphene oxide solution, ultrasonically stirring for 4 hours, and transferring into a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the thermosetting polybenzoxazine enhanced graphene hydrogel. And washing and freeze-drying the hydrogel for 48 hours to obtain the polybenzoxazine reinforced three-dimensional graphene foam. Then placing the polybenzoxazine enhanced three-dimensional graphene foam into a quartz tube, heating to 350 ℃ under the protection of 200sccm argon gas, carrying out annealing treatment for 3 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 26mg/cm3A specific surface area of 513m2(ii)/g, conductivity 57S/m.
Comparative example 1
Firstly, graphene oxide is prepared by an improved Hummers method, a 4mg/ml graphene oxide aqueous solution (50ml) is prepared by ultrasonic and mechanical stirring, and the solution is transferred into a reaction kettle at 160 DEG CReacting for 8 hours under the condition to obtain hydrogel, freeze-drying the hydrogel for 48 hours to obtain three-dimensional graphene aerogel, then placing polybenzoxazine enhanced three-dimensional graphene foam into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon, annealing for 3 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel. The aerogel has a density of 15mg/cm3A specific surface area of 123m2The electrical conductivity was 36S/m.
Comparative example 2
Firstly, graphene oxide GO is prepared by adopting an improved Hummers method, a 4mg/ml graphene oxide aqueous solution (50ml) is prepared by means of ultrasonic and mechanical stirring, then a 20% acetone solution (2.0ml) of 3, 4-dihydro-1, 3 benzoxazine is slowly dripped (1 ml/min) into the graphene oxide dispersion liquid, and the graphene oxide GO is transferred into a reaction kettle after ultrasonic and stirring for 6 hours. And (3) reacting the reaction kettle filled with the mixed solution at the temperature of 100 ℃ for 6 hours to obtain the polybenzoxazine enhanced graphene hydrogel. And washing and freeze-drying the hydrogel for 48 hours to obtain the polybenzoxazine reinforced three-dimensional graphene foam. Then placing the polybenzoxazine enhanced three-dimensional graphene foam into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon gas, carrying out annealing treatment for 3 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 54mg/cm3Specific surface area of 176m2The electrical conductivity was 36S/m.
Table 1 shows the preparation methods and performance parameters of the three-dimensional graphene aerogels prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention:
the foregoing is merely an example of the present invention and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of polybenzoxazine reinforced three-dimensional graphene foam is characterized by comprising the following steps:
dripping an organic solution containing a benzoxazine monomer into a graphene oxide aqueous solution and uniformly mixing to obtain a mixed solution;
carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 80-210 ℃ for 6-48 hours, and then washing and drying to obtain the polybenzoxazine enhanced three-dimensional graphene foam.
2. The preparation method according to claim 1, wherein the concentration of the graphene oxide aqueous solution is 1mg/ml to 15 mg/ml; preferably, the graphene oxide is prepared by adopting a modified Hummers method.
3. The preparation method according to claim 1 or 2, characterized in that the mass concentration of the benzoxazine monomer in the organic solution containing the benzoxazine monomer is 0.4-30%.
4. The production method according to any one of claims 1 to 3, wherein the benzoxazine monomer is selected from at least one of 3, 4-dihydro-1, 3 benzoxazine, bisphenol A type benzoxazine, diphenylmethane diamine type benzoxazine, polycyclic benzoxazine, and diallyl dibenzooxazine.
5. The preparation method according to any one of claims 1 to 4, wherein the benzoxazine monomer accounts for 0.5 to 60 percent of the mass of the graphene oxide.
6. The method according to any one of claims 1 to 5, wherein the organic solvent in the organic solution containing benzoxazine monomer is at least one of acetone, diethyl ether, dimethylformamide, dimethyl sulfoxide, toluene, xylene, dichloromethane and chloroform.
7. The production method according to any one of claims 1 to 6, wherein the dropping is performed at a rate of 0.5 to 5 ml/min.
8. The method according to any one of claims 1 to 7, wherein the drying is performed by one of freeze drying, vacuum drying and supercritical drying.
9. The three-dimensional graphene aerogel is characterized in that the polybenzoxazine reinforced three-dimensional graphene foam prepared according to the preparation method of any one of claims 1-8 is subjected to annealing treatment at 200-1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811250877.0A CN111100291B (en) | 2018-10-25 | 2018-10-25 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811250877.0A CN111100291B (en) | 2018-10-25 | 2018-10-25 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111100291A true CN111100291A (en) | 2020-05-05 |
| CN111100291B CN111100291B (en) | 2021-08-31 |
Family
ID=70417842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811250877.0A Active CN111100291B (en) | 2018-10-25 | 2018-10-25 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111100291B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010982A (en) * | 2022-07-11 | 2022-09-06 | 江西理工大学 | Polybenzoxazine aerogel taking water as solvent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691449A (en) * | 2009-09-04 | 2010-04-07 | 广东生益科技股份有限公司 | Method for improving flame retarding efficiency of phenoxy phosphazene compound and prepreg, laminated board and printed circuit laminated board prepared by same |
| CN102219785A (en) * | 2011-04-11 | 2011-10-19 | 山东大学 | Triazine-containing benzoxazine, triazine-containing benzoxazine polymer, and preparation method thereof |
| CN103613096A (en) * | 2013-12-06 | 2014-03-05 | 福州大学 | Low-cost method for preparing graphene macroform |
| CN105111437A (en) * | 2015-09-28 | 2015-12-02 | 中国地质大学（武汉） | Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof |
| CN106082170A (en) * | 2016-06-15 | 2016-11-09 | 泰山医学院 | A kind of benzoxazine resins base carbon aerogels and preparation method thereof |
| CN106422995A (en) * | 2015-08-11 | 2017-02-22 | 中国科学院化学研究所 | Graphene aerogel and hybrid composite material thereof as well as preparation method and application of graphene aerogel |
| CN107603475A (en) * | 2017-09-06 | 2018-01-19 | 济南大学 | A kind of bisphenol AF PEG block copolymer hydrophilic surface coating and preparation method thereof |
-
2018
- 2018-10-25 CN CN201811250877.0A patent/CN111100291B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691449A (en) * | 2009-09-04 | 2010-04-07 | 广东生益科技股份有限公司 | Method for improving flame retarding efficiency of phenoxy phosphazene compound and prepreg, laminated board and printed circuit laminated board prepared by same |
| CN102219785A (en) * | 2011-04-11 | 2011-10-19 | 山东大学 | Triazine-containing benzoxazine, triazine-containing benzoxazine polymer, and preparation method thereof |
| CN103613096A (en) * | 2013-12-06 | 2014-03-05 | 福州大学 | Low-cost method for preparing graphene macroform |
| CN106422995A (en) * | 2015-08-11 | 2017-02-22 | 中国科学院化学研究所 | Graphene aerogel and hybrid composite material thereof as well as preparation method and application of graphene aerogel |
| CN105111437A (en) * | 2015-09-28 | 2015-12-02 | 中国地质大学（武汉） | Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof |
| CN106082170A (en) * | 2016-06-15 | 2016-11-09 | 泰山医学院 | A kind of benzoxazine resins base carbon aerogels and preparation method thereof |
| CN107603475A (en) * | 2017-09-06 | 2018-01-19 | 济南大学 | A kind of bisphenol AF PEG block copolymer hydrophilic surface coating and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ALMAHDI A. ALHWAIGE等: ""Interactions, morphology and thermal stability of graphene-oxide reinforced polymer aerogels derived from star-like telechelic aldehyde-terminal benzoxazine resin"", 《RSC ADVANCES》 * |
| 郭松柏等主编: "《纳米与材料》", 30 April 2018, 苏州大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010982A (en) * | 2022-07-11 | 2022-09-06 | 江西理工大学 | Polybenzoxazine aerogel taking water as solvent and preparation method thereof |
| CN115010982B (en) * | 2022-07-11 | 2023-04-25 | 江西理工大学 | Polybenzoxazine aerogel taking water as solvent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111100291B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Macroscopic-scale preparation of aramid nanofiber aerogel by modified freezing–drying method | |
| Gong et al. | Amino graphene oxide/dopamine modified aramid fibers: Preparation, epoxy nanocomposites and property analysis | |
| Hu et al. | Tough and stretchable Fe3O4/MoS2/PAni composite hydrogels with conductive and magnetic properties | |
| CN108504096B (en) | Preparation method of carbon nano tube/polymer composite material | |
| CN105597791B (en) | A kind of selenizing molybdenum/porous carbon nanofiber composite material and preparation method and application | |
| CN109400960B (en) | Graphene/nano-silver polymer composite material and preparation method thereof | |
| CN108516538B (en) | Preparation method of pi-bond and covalent-bond orderly-crosslinked superstrong high-conductivity graphene composite film | |
| Zhang et al. | Highly compressible, thermally conductive, yet electrically insulating fluorinated graphene aerogel | |
| Wu et al. | Nondestructive strategy to effectively enhance the interfacial adhesion of PBO/epoxy composites | |
| KR101804577B1 (en) | Carbon nanotube fibers and method of preparing the same | |
| CN111218113A (en) | g-C3N4CNT (carbon nano tube) nano hybrid material modified PPESK (Polytetrafluoroethylene-styrene-ethylene-styrene) lubricating film and preparation method thereof | |
| CN107604482B (en) | A kind of N doping porous filamentous nanocarbon and preparation method thereof | |
| CN114197205B (en) | Modified carbon fiber and preparation method and application thereof | |
| Gong et al. | An emerging class of carbon materials: Synthesis and applications of carbon flowers | |
| CN113527753A (en) | Bio-based foam material prepared under normal pressure and preparation method and application thereof | |
| Zhang et al. | Influence of acid-base catalysis on the textural and thermal properties of carbon aerogel monoliths | |
| CN111100291B (en) | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam | |
| CN111498827B (en) | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof | |
| Wei et al. | Polyarylene ether nitrile and boron nitride composites: coating with sulfonated polyarylene ether nitrile | |
| Shen et al. | Efficient reinforcement of epoxy resin with amine‐rich rigid short‐chain grafted graphene oxide | |
| Qin et al. | Preparing nitrogen-doped multiwalled carbon nanotubes with regionally controllable heterojunction structure by nondestructive postdoping with the assistance of heating fluorination | |
| CN114773684A (en) | Chemically crosslinked cellulose-based composite foam and preparation method and application thereof | |
| Fan et al. | Highly elastic photothermal nanofibrillated cellulose aerogels for solar-assisted efficient cleanup of viscous oil spill | |
| Jiang et al. | Use of ionic monomers to prepare halloysite polymer nanocomposites with reinforced mechanical performance | |
| CN113583442A (en) | Preparation method of self-repairing polyimide composite material with photo-thermal performance for additive manufacturing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |