CN113248738B - Two-dimensional material modified epoxy resin composite material and preparation method thereof - Google Patents
Two-dimensional material modified epoxy resin composite material and preparation method thereof Download PDFInfo
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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Abstract
The invention provides a two-dimensional material modified epoxy resin composite material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) dispersing the cation modified two-dimensional material in water to obtain a two-dimensional material dispersion liquid; (2) uniformly mixing epoxy resin and aromatic glycidyl ether, adding the two-dimensional material dispersion liquid obtained in the step (1), and performing a phase transfer process to obtain a mixture; (3) and (3) adding an amine curing agent into the mixture obtained in the step (2), mixing, pouring into a preheating mold, and curing to obtain the two-dimensional material modified epoxy resin composite material. The invention also comprises the composite material prepared by the method. The invention improves the dispersibility and compatibility of the two-dimensional material in the epoxy resin substrate, thereby improving the strength and toughness of the composite material, effectively solving the problems of contradiction between the strength and the toughness, reduced ductility and the like of the epoxy resin composite material in the prior art, and being suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of epoxy resin composite materials, and particularly relates to a two-dimensional material modified epoxy resin composite material and a preparation method thereof.
Background
The epoxy resin belongs to thermosetting resin, has the advantages of excellent adhesive property, easy processing, low cost, light weight, heat resistance, chemical resistance and the like, and shows great potential in the aspects of biological medical treatment, electronic information, aerospace and the like. However, the epoxy resin has the main defects of high crosslinking density, brittle quality, insufficient toughness and the like, and the application of the epoxy resin in an environment with higher toughness is seriously influenced. In order to improve the mechanical properties of epoxy resins, nanomaterials (e.g., silica, carbon materials, metal hydroxides, etc.) are often added to the epoxy resins. The two-dimensional material has a wide application prospect in the field of epoxy resin composite materials due to the advantages of ultrahigh specific surface area, excellent mechanical properties, extremely high Young modulus, thermal stability and the like. However, in the epoxy resin matrix, van der waals forces between the two-dimensional material sheets tend to cause poor dispersion and even severe agglomeration in the composite, especially at high filler contents, thereby affecting the properties of the epoxy resin composite. Therefore, it is still a great challenge to produce high-toughness two-dimensional material/epoxy resin composite material with low cost and high efficiency.
The surface covalent and non-covalent modification of the two-dimensional material can improve the dispersion performance and compatibility of the two-dimensional material in an epoxy matrix, thereby improving the mechanical performance of the epoxy resin composite material. At present, the contradiction between strength and toughness exists in the epoxy resin composite material modified by a two-dimensional material, and the ductility is reduced due to the improvement of the strength of the composite material. In addition, the dispersion of the modified two-dimensional material in the epoxy resin usually requires the use of organic solvents and time-consuming sample preparation steps, which is not suitable for industrial production. In view of the above disadvantages of the two-dimensional material modified epoxy resin composite material, there is an urgent need in the industry to develop a new method for preparing a high-toughness two-dimensional material modified epoxy resin composite material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the two-dimensional material modified epoxy resin composite material and the preparation method thereof, which improve the dispersibility and compatibility of the two-dimensional material in the epoxy resin substrate, thereby improving the strength and toughness of the composite material, effectively solving the problems of contradiction between the strength and toughness, reduced ductility and the like of the epoxy resin composite material in the prior art, and being suitable for industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing the cation modified two-dimensional material in water to obtain a two-dimensional material dispersion liquid;
(2) uniformly mixing epoxy resin and aromatic glycidyl ether, adding the two-dimensional material dispersion liquid obtained in the step (1), and performing a phase transfer process to obtain a mixture;
(3) and (3) adding an amine curing agent into the mixture obtained in the step (2), mixing, pouring into a preheating mold, and curing to obtain the two-dimensional material modified epoxy resin composite material.
Further, the preparation method of the two-dimensional material modified epoxy resin composite material specifically comprises the following steps:
(1) dispersing the cation modified two-dimensional material in water to obtain a two-dimensional material dispersion liquid;
(2) mixing epoxy resin and aromatic glycidyl ether, stirring for 1-2h at the temperature of 35-45 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) adding an amine curing agent into the mixture obtained in the step (2), magnetically stirring at room temperature for 4-6min, then carrying out vacuum degassing for 20-40min, pouring into a preheated polytetrafluoroethylene mold, and curing at the temperature of 70-90 ℃ for 10-15h to obtain the two-dimensional material modified epoxy resin composite material.
Further, in the step (1), the cation modified two-dimensional material is prepared by the following method: dispersing graphene oxide in an alkaline solution or an ionic liquid aqueous solution, standing for 1-3h, then adding hydrazine hydrate under the condition of magnetic stirring, heating for 1-3h at the temperature of 100 ℃, and standing for 1-3h at room temperature to obtain the cation modified two-dimensional material.
Further, the mass ratio of the graphene oxide to the hydrazine hydrate is 1: 50.
Further, the concentration of the solution after the graphene oxide is dispersed is 300 mg/L.
Further, in the step (1), the cation modified two-dimensional material is prepared by the following method: and dispersing the metal carbide in an alkaline solution or an ionic liquid aqueous solution, and standing for 1-3h to obtain the cation modified two-dimensional material.
Further, the concentration of the solution after dispersion of the metal carbide was 30 mg/L.
Further, the pH of the alkaline solution was 10, and the concentration of the ionic liquid aqueous solution was 0.05M.
Further, in the step (2), the epoxy resin is bisphenol a epoxy resin, bisphenol F epoxy resin, E44 or E51.
Further, in the step (2), the aromatic glycidyl ether is benzyl glycidyl ether or indolyl glycidyl ether.
Further, in the step (2), the molar ratio of the aromatic glycidyl ether monomer to the epoxy resin monomer is 1: 5.
Further, in the step (3), the amine curing agent is ethylenediamine, triethylenetetramine, diethylenetriamine, tetraethylenepentamine or polyetheramine.
Further, the amount of the amine-based curing agent was calculated from the stoichiometric ratio of active hydrogen to epoxy group 1: 1.
Further, the mass fraction of the cation modified two-dimensional material in the composite material is 0-2 wt%.
The two-dimensional material modified epoxy resin composite material is prepared by the preparation method of the two-dimensional material modified epoxy resin composite material.
In summary, the invention has the following advantages:
1. the invention improves the dispersibility and compatibility of the two-dimensional material in the epoxy resin substrate, thereby improving the strength and toughness of the composite material, endowing the composite material with more functionality, effectively solving the problems of contradiction between the strength and toughness, reduced ductility and the like of the epoxy resin composite material in the prior art, and being suitable for industrial production.
2. Generally, the two-dimensional material is required to be dispersed in an organic solvent when the two-dimensional material is introduced into the epoxy resin, so that a green pollution-free generation process cannot be realized, and the two-dimensional material graphene can only be dispersed in the organic solvent and is difficult to disperse in an aqueous solution. According to the invention, the two-dimensional material can be well dispersed in the aqueous solution through the cation modified two-dimensional material, the cation-pi interaction between the indole group and the cation modified two-dimensional material not only promotes the cation modified two-dimensional material to be transferred from a water phase to an organic phase, but also enables the two-dimensional material to be uniformly dispersed in the epoxy resin, avoids the phenomenon of agglomeration of the two-dimensional material in an epoxy matrix, improves the dispersibility and the interface compatibility between the two-dimensional material and the epoxy resin, is green and environment-friendly in the preparation process, does not need to introduce additional solvents, and meets the requirements of sustainable development at present.
3. The invention can continuously break and reconstruct under the external field stimulation by introducing dynamic bonds between the filler and the epoxy substrate, so that the composite material can show good energy dissipation effect while ensuring the structural integrity, and can avoid the contradiction between the strength and the toughness commonly existing in the epoxy resin composite material; and the cation-pi interaction dynamic bond between the indole group and the cation modified two-dimensional material belongs to a 'surface-surface' action form, and compared with a reported 'point-surface' cation-pi interaction form, the 'surface-surface' cation-pi interaction form has larger combination area, is easier to reconstruct after fracture, is easier to overcome the contradiction between strength and toughness commonly existing in the epoxy resin composite material, and greatly improves the mechanical properties of the epoxy resin composite material, for example, compared with pure epoxy resin, the tensile strength and the elongation at break of the potassium modified graphene/epoxy resin composite material are respectively improved by 126% and 117%.
4. The two-dimensional material modified epoxy resin composite material has simple preparation process and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an FT-IR spectrum of indolyl glycidyl ether;
FIG. 2 is an SEM image of a two-dimensional material before and after cationic modification;
FIG. 3 is a stress-strain curve for a pure epoxy resin and different levels of two-dimensional material modified epoxy resin composite;
FIG. 4 is a SEM image of a cross section of a composite material of pure epoxy resin and two-dimensional material modified epoxy resin with different contents.
Detailed Description
The following examples take indolyl glycidyl ether as an example, and the specific synthetic process is as follows:
dissolving 2.34g of indole in 23.5mL of epoxy chloropropane under the atmosphere of nitrogen, and then adding powdery potassium hydroxide; stirring for 3h at 60 ℃, after the reaction is finished, filtering to remove potassium hydroxide powder, distilling under reduced pressure to remove epichlorohydrin, and purifying the crude product by using a chromatographic column separation method to obtain the indolyl glycidyl ether.
The reaction process is as follows:
an infrared spectrum of the obtained indolyl glycidyl ether is obtained, as shown in figure 1.
As can be seen from FIG. 1, 1314cm-1The nearby characteristic peak is attributed to the telescopic vibration of indole ring, 910cm-1The characteristic peak at (A) is attributed to the stretching vibration of C-O-C, 746cm-1The absorption peak is the C-H vibration out of the plane of the benzene ring, and the results indicate the successful preparation of the indolyl glycidyl ether monomer.
Example 1
A preparation method of a two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing graphene oxide in a KOH solution with the pH value of 10 to obtain a dispersion liquid with the concentration of 300mg/L, standing the dispersion liquid for 2h, then adding hydrazine hydrate under magnetic stirring, heating at 100 ℃ for 2h, and standing at room temperature for 2h to obtain potassium ion modified graphene; dispersing the potassium ion modified graphene in water to obtain a two-dimensional material dispersion liquid;
(2) weighing aromatic glycidyl ether (such as indolyl glycidyl ether monomer (IN)) and epoxy resin monomer (such as bisphenol A epoxy resin DGEBA) IN a molar ratio of 1:5 IN a beaker, stirring for 1h at 40 ℃, adding the two-dimensional material dispersion liquid obtained IN the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) violently stirring the mixture obtained in the step (2) at 40 ℃ for 4h, then drying the mixture at 80 ℃ in vacuum for 4h, adding a curing agent (such as triethylene tetramine) into the mixed phase, magnetically stirring the mixture at room temperature for 5min, then degassing the mixture in a vacuum oven for 30min, finally pouring the mixture into a preheated polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 12h to obtain the two-dimensional material modified epoxy resin composite material.
Example 2
A preparation method of a two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing graphene oxide in a NaOH solution with the pH value of 10 to obtain a dispersion liquid with the concentration of 300mg/L, standing the dispersion liquid for 2h, then adding hydrazine hydrate under magnetic stirring, heating at 100 ℃ for 2h, and standing at room temperature for 2h to obtain sodium ion modified graphene; dispersing sodium ion modified graphene in water to obtain a two-dimensional material dispersion liquid;
(2) weighing an aromatic glycidyl ether monomer and an epoxy resin monomer in a molar ratio of 1:5 in a beaker, stirring for 1h at 40 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until a water phase is colorless and transparent to obtain a mixture;
(3) and (3) violently stirring the mixture obtained in the step (2) at 40 ℃ for 4h, then drying the mixture at 80 ℃ in vacuum for 4h, adding a curing agent (such as triethylene tetramine) into the mixed phase, magnetically stirring the mixture at room temperature for 5min, then degassing the mixture in a vacuum oven for 30min, finally pouring the mixture into a preheated polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 12h to obtain the two-dimensional material modified epoxy resin composite material.
Example 3
A preparation method of a two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing graphene oxide in 0.05M imidazole cation solution to obtain dispersion liquid with the concentration of 300mg/L, standing the dispersion liquid for 2 hours, then adding hydrazine hydrate under magnetic stirring, heating at 100 ℃ for 2 hours, and standing at room temperature for 2 hours to obtain imidazole cation modified graphene; dispersing imidazole cation modified graphene in water to obtain a two-dimensional material dispersion liquid;
(2) weighing an aromatic glycidyl ether monomer and an epoxy resin monomer with a molar ratio of 1:5 in a beaker, stirring for 1h at 40 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) violently stirring the mixture obtained in the step (2) at 40 ℃ for 4h, then drying the mixture at 80 ℃ in vacuum for 4h, adding a curing agent (such as triethylene tetramine) into the mixed phase, magnetically stirring the mixture at room temperature for 5min, then degassing the mixture in a vacuum oven for 30min, finally pouring the mixture into a preheated polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 12h to obtain the two-dimensional material modified epoxy resin composite material.
Example 4
A preparation method of a two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing metal carbide in a 1M KOH solution to obtain a dispersion liquid with the concentration of 30mg/L, and standing the dispersion liquid for 2 hours to obtain potassium ion modified metal carbide; dispersing potassium ion modified metal carbide in water to obtain two-dimensional material dispersion liquid;
(2) weighing an aromatic glycidyl ether monomer and an epoxy resin monomer with a molar ratio of 1:5 in a beaker, stirring for 1h at 40 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) violently stirring the mixture obtained in the step (2) at 40 ℃ for 4h, then drying the mixture at 80 ℃ in vacuum for 4h, adding a curing agent (such as triethylene tetramine) into the mixed phase, magnetically stirring the mixture at room temperature for 5min, then degassing the mixture in a vacuum oven for 30min, finally pouring the mixture into a preheated polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 12h to obtain the two-dimensional material modified epoxy resin composite material.
Example 5
A preparation method of a two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing the metal carbide in a 1M NaOH solution to obtain a dispersion liquid with the concentration of 30mg/L, and standing the dispersion liquid for 2 hours to obtain a sodium ion modified metal carbide; dispersing sodium ion modified metal carbide in water to obtain two-dimensional material dispersion liquid;
(2) weighing an aromatic glycidyl ether monomer and an epoxy resin monomer with a molar ratio of 1:5 in a beaker, stirring for 1h at 40 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) violently stirring the mixture obtained in the step (2) at 40 ℃ for 4h, then drying the mixture at 80 ℃ in vacuum for 4h, adding a curing agent (such as triethylene tetramine) into the mixed phase, magnetically stirring the mixture at room temperature for 5min, then degassing the mixture in a vacuum oven for 30min, finally pouring the mixture into a preheated polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 12h to obtain the two-dimensional material modified epoxy resin composite material.
Example 6
A preparation method of a two-dimensional material modified epoxy resin composite material comprises the following steps:
(1) dispersing metal carbide in 0.05M imidazole cation solution to obtain dispersion liquid with the concentration of 30mg/L, and standing the dispersion liquid for 2 hours to obtain imidazole cation modified metal carbide; dispersing imidazole cation modified metal carbide in water to obtain a two-dimensional material dispersion liquid;
(2) weighing an aromatic glycidyl ether monomer and an epoxy resin monomer with a molar ratio of 1:5 in a beaker, stirring for 1h at 40 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) violently stirring the mixture obtained in the step (2) at 40 ℃ for 4h, then drying the mixture at 80 ℃ in vacuum for 4h, adding a curing agent (such as triethylene tetramine) into the mixed phase, magnetically stirring the mixture at room temperature for 5min, then degassing the mixture in a vacuum oven for 30min, finally pouring the mixture into a preheated polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 12h to obtain the two-dimensional material modified epoxy resin composite material.
Examples of the experiments
SEM images of the graphene before and after the potassium ion modification in example 1 were obtained, and the results are shown in fig. 2.
As can be seen from FIG. 2, the graphene (K-rGO) still has a lamellar structure after the modification of potassium ions.
According to the preparation method in the example 1, pure epoxy resin and two-dimensional material modified epoxy resin composite materials with different contents are respectively obtained, and corresponding stress-strain curves (figure 3) and mechanical properties (table 1) are obtained. In Table 1, EP20-0.05K-rGO represents that the content of indolyl glycidyl ether is 20 mol%, the content of potassium ion modified graphene (K-rGO) is 0.05 wt%, and so on.
TABLE 1 mechanical Properties of two-dimensional Material modified epoxy resin composites with different contents
| Sample (I) | Tensile Strength (MPa) | Elongation at Break (%) |
| EP0 | 62.8 | 6.8 |
| EP20 | 87.9 | 8.4 |
| EP20-0.05K-rGO | 120.8 | 11.1 |
| EP20-0.10K-rGO | 136.0 | 15.4 |
| EP20-0.15K-rGO | 127.9 | 14.3 |
| EP20-0.20K-rGO | 129.7 | 12.7 |
As can be seen from Table 1, the tensile strength and the elongation at break of the pure epoxy resin are the lowest, and the tensile strength and the elongation at break of the pure epoxy resin are obviously improved after the potassium ion modified graphene is doped.
As can be seen from fig. 3, when the doping amount of the potassium ion-modified graphene is 0.1 wt%, the tensile strength and the elongation at break both reach maximum values, which are 15.4% and 136.0MPa, respectively, compared to the pure epoxy resin (EP0), and the tensile strength and the elongation at break are respectively increased by 126% and 117% compared to the pure epoxy resin.
Meanwhile, SEM images of the cross sections of the pure epoxy resin and the two-dimensional material modified epoxy resin composite material with different contents were obtained, respectively, as shown in fig. 4.
As can be seen from fig. 4, due to the inherent brittleness of pure epoxy (EP0), the fracture surface was relatively smooth and in a clear river-like morphology after crack propagation. The cleavage surface of the indolyl glycidyl ether modified epoxy resin (EP20) is also relatively smooth. However, after the potassium ion modified graphene is introduced into the epoxy matrix (EP20-0.05K-rGO, EP20-0.1K-rGO, EP20-0.15K-rGO, EP20-0.2K-rGO), the fracture surface of the epoxy resin shows different characteristics, and the fracture surface of the epoxy resin composite material becomes rougher as the content of the potassium ion modified graphene increases. In addition, no obvious aggregation of the potassium ion modified graphene nanosheets is observed in the cross section of the epoxy nanocomposite, which indicates that the potassium ion modified graphene nanosheets are highly dispersed in the epoxy matrix; gaps between the potassium ion modified graphene nanosheets and the epoxy matrix are not observed on the fractured surfaces, which indicates that good interaction exists between the potassium ion modified graphene nanosheets and the epoxy matrix interface. The high dispersibility and good interface bonding of the potassium ion modified graphene nanosheets can be attributed to a strong cation-pi interaction between the potassium ion modified graphene nanosheets and the indolyl groups, which is also one of the important reasons for improving the fracture toughness of the epoxy resin. In addition, the high compatibility of the potassium ion modified graphene nanosheet and the epoxy matrix enables stress transfer between the graphene nanosheet and the epoxy matrix to be more effective, higher load is borne, more energy is consumed, and therefore the mechanical property of the composite material is improved.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (6)
1. A preparation method of a two-dimensional material modified epoxy resin composite material is characterized by comprising the following steps:
(1) dispersing the cation modified two-dimensional material in water to obtain two-dimensional material dispersion liquid;
(2) uniformly mixing epoxy resin and aromatic glycidyl ether, adding the two-dimensional material dispersion liquid obtained in the step (1), and performing a phase transfer process to obtain a mixture; the epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, E44 or E51; the aromatic glycidyl ether is benzyl glycidyl ether or indolyl glycidyl ether;
(3) adding an amine curing agent into the mixture obtained in the step (2), mixing, pouring into a preheating mold, and curing to obtain a two-dimensional material modified epoxy resin composite material;
in the step (1), the cation modified two-dimensional material is prepared by the following method: dispersing graphene oxide in an alkaline solution or an ionic liquid aqueous solution, standing for 1-3h, then adding hydrazine hydrate under the condition of magnetic stirring, heating for 1-3h at the temperature of 100 ℃, and standing for 1-3h at room temperature to obtain a cation modified two-dimensional material;
or the cation modified two-dimensional material is prepared by the following method: dispersing metal carbide in an alkaline solution or an ionic liquid aqueous solution, and standing for 1-3h to obtain a cation modified two-dimensional material;
the alkaline solution is a potassium hydroxide solution or a sodium hydroxide solution.
2. The method for preparing the two-dimensional material modified epoxy resin composite material according to claim 1, comprising the following steps:
(1) dispersing the cation modified two-dimensional material in water to obtain a two-dimensional material dispersion liquid;
(2) mixing epoxy resin and aromatic glycidyl ether, stirring for 1-2h at the temperature of 35-45 ℃, then adding the two-dimensional material dispersion liquid obtained in the step (1), and stirring at room temperature until the water phase is colorless and transparent to obtain a mixture;
(3) and (3) adding an amine curing agent into the mixture obtained in the step (2), magnetically stirring at room temperature for 4-6min, then carrying out vacuum degassing for 20-40min, pouring into a preheated polytetrafluoroethylene mold, and curing at the temperature of 70-90 ℃ for 10-15h to obtain the two-dimensional material modified epoxy resin composite material.
3. The method for preparing a two-dimensional material modified epoxy resin composite material according to claim 1 or 2, wherein in the step (2), the aromatic glycidyl ether and the epoxy resin are in a molar ratio of 1: 5.
4. The method for preparing the two-dimensional material modified epoxy resin composite material according to claim 1 or 2, wherein in the step (3), the amine curing agent is ethylenediamine, triethylenetetramine, diethylenetriamine, tetraethylenepentamine or polyetheramine.
5. The method for preparing a two-dimensional material modified epoxy resin composite material according to claim 1 or 2, wherein the mass fraction of the cation-modified two-dimensional material in the composite material is 0.05 to 2 wt%.
6. The two-dimensional material modified epoxy resin composite material prepared by the method for preparing the two-dimensional material modified epoxy resin composite material according to any one of claims 1 to 5.
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| US20120296012A1 (en) * | 2010-02-04 | 2012-11-22 | Drexel University | Room temperature ionic liquid-epoxy systems as dispersants and matrix materials for nanocomposites |
| CN103819880B (en) * | 2014-03-20 | 2016-02-03 | 江南大学 | Method for modifying graphene modified epoxy resin by amphiphilic copolymer |
| CN104448239B (en) * | 2014-10-11 | 2017-02-22 | 浙江大学 | High-strength epoxy resin composite material and preparation method thereof |
| GB201611165D0 (en) * | 2016-06-27 | 2016-08-10 | Univ Limerick | Adhesive composition |
| CN107245224A (en) * | 2017-08-02 | 2017-10-13 | 四川亿家空间环保科技有限公司 | A kind of graphene nanocomposite material and preparation method thereof |
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| CN108424613A (en) * | 2018-02-02 | 2018-08-21 | 桂林理工大学 | A kind of preparation method of ion liquid modified graphene/carbon nano-tube/epoxy resin composite material |
| CN109456678A (en) * | 2018-11-19 | 2019-03-12 | 福建师范大学泉港石化研究院 | A kind of graphene modification method for preparing suitable for epoxy resin |
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