CN112521716B - Graphene aerogel-polyimide composite membrane material and preparation method thereof - Google Patents
Graphene aerogel-polyimide composite membrane material and preparation method thereof Download PDFInfo
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- CN112521716B CN112521716B CN202011472736.0A CN202011472736A CN112521716B CN 112521716 B CN112521716 B CN 112521716B CN 202011472736 A CN202011472736 A CN 202011472736A CN 112521716 B CN112521716 B CN 112521716B
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a graphene aerogel-polyimide composite membrane material and a preparation method thereof, and relates to the field of flexible electronics. The composite material comprises the following raw materials in mass ratio of 1:6-1: the 200 graphene aerogel and polyimide are prepared by adopting a mechanical mixing and chemical crosslinking mode, graphene oxide is prepared by utilizing an improved hummers method, then the graphene oxide is reduced into graphene hydrogel through a hydrothermal method, and then the graphene aerogel is obtained by means of the processes of directional freezing-freeze drying and high-temperature annealing. On the basis, the graphene aerogel is uniformly dispersed into a solution, then a dialdehyde compound, a diamine compound and a cross-linking agent triamine compound are sequentially added, the materials are uniformly mixed and poured into a mold, the solvent is evaporated by gradient temperature rise to dryness to form a film, the obtained film not only keeps the layered structure and excellent conductivity of the graphene aerogel, but also can realize repairability and recycling by means of the reversibility of imine bonds, and a new idea is provided for the sustainable development direction of flexible electronic materials.
Description
Technical Field
The invention relates to the field of conductive materials, in particular to a graphene aerogel-polyimide composite membrane material and a preparation method thereof.
Background
The polyimide resin is a novel thermosetting material, and belongs to the class of body type high polymer materials. The polyimide resin is formed by aldehyde-amine condensation reaction and imine exchange reaction under the drive of water and (or) heat, and the dynamic covalent interaction of imine bonds ensures that the polyimide has excellent performances such as malleable plasticity, repairability and recyclability. The polyimine can be easily self-repaired at room temperature by hot press molding or solvent wetting conditions. In addition, different precursors for synthesizing polyimides can impart different mechanical properties to polyimide materials, and thus are widely used. However, pure polyimide is an insulating material, and further application of the polyimide is limited, so that modification of polyimide resin to make the polyimide resin have conductivity is an important direction for expanding application of the polyimide resin.
The graphene aerogel has the characteristics of ultralow density and ultrahigh porosity, has excellent conductive property, and has a remarkable reinforcing effect on a high-molecular base material.
Disclosure of Invention
The invention aims to provide a graphene aerogel-polyimide composite film material which has the conductivity of graphene aerogel and the repairability and the recycling performance of polyimide resin.
The invention adopts the following technical scheme:
graphene aerogel-polyimide composite membrane material, its characterized in that this composite membrane material contains polyimide and graphene aerogel, and its mass ratio is 6:1-200:1.
the preparation method of the graphene aerogel-polyimide composite membrane material is characterized by comprising the following steps:
the mass ratio of dialdehyde to graphene aerogel is 3:1-130:1, the concentration of the solute and the solvent is 30 mg/ml-150 mg/ml;
the molar ratio of diamine compound to triamine compound in the second solution is 3:5-4:5, the concentration of the solute and the solvent is 20 mg/ml-210 mg/ml; the molar ratio of dialdehyde compound to triamine compound in the mixture of the first solution and the second solution is 2:1-3:1;
placing 0.5-3 h at room temperature, and changing the film from a solution state to a latex state;
then heating to 40 ℃ and keeping 0.5-3 h, and changing the film from emulsion to colloid;
continuously heating to 60-65 ℃, and preserving heat for 4-12 h;
then heating to 75-80 ℃, and preserving heat for 2-4 h;
finally, heating to 85-90 ℃, and preserving heat for 2-4 h;
and 4, carrying out hot pressing treatment on the film, and carrying out hot pressing on the film at 80-100 ℃ for 1-6 h.
The organic solvent having better solubility to the dialdehyde compound described in steps 1 and 2 includes N, N-dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, dichloromethane or ethanol.
The diamine compound amine source comprises diethylenetriamine, tri (2-aminoethyl) amine, ethylenediamine or 2,2' -diamino-N-methyldiethanamine).
The triamine compound crosslinking agent comprises diethylenetriamine or tri (2-aminoethyl) amine.
The mass ratio of the polyimide to the graphene aerogel is less than 6:1, the resulting film may be cracked, failing to ensure the quality of the film.
The composite material is prepared by modifying polyimide with the graphene aerogel, so that the composite material has the conductivity of the graphene aerogel and the repairability and recovery performance of the polyimide, and has excellent comprehensive performance. When the composite material is used for a flexible electronic device, the electrical conductivity is excellent, the material can be repaired and recovered, and the generation of electronic waste is reduced. In the preparation method, the polyimide is synthesized and modified by the graphene aerogel, so that the modification efficiency can be effectively improved, and meanwhile, the semi-finished product is treated in a gradient heating manner, so that the comprehensive performance of the material is effectively improved.
Compared with the existing graphene aerogel modified by polyethyleneimine, the polyethyleneimine is a common polymer, and the polyethyleneimine is a dynamic covalent chemical polymer, so that the self-repairing and recycling performances of the composite material can be ensured. In the preparation process, the modified graphene aerogel is prepared by mixing a polymer and graphene oxide (a precursor of the graphene aerogel) and then forming the aerogel by a hydrothermal method, wherein the polyimide is prepared by carrying out in-situ polymerization reaction on monomers in the presence of the aerogel.
Different from the existing method for preparing the graphene aerogel after amine substances are rechecked in the graphene aerogel, the method provided by the invention adopts a mode of directly rechecking the graphene aerogel and the polyimide. The polyimide is a self-repairing material, so that the repair of the composite material and the complete recovery of each component can be realized compared with the existing amine substance modified graphene aerogel. And the amine substance modified graphene aerogel can only improve the mechanical strength and prolong the service life.
Drawings
Fig. 1 is a cross-sectional scanning electron microscope image of the graphene aerogel-polyimide composite film in example 2 of the present invention.
Fig. 2 is an optical image of a graphene aerogel-polyimide composite film before and after repair in example 2 of the present invention.
Fig. 3 is a schematic view of recycling of the graphene aerogel-polyimide composite film in embodiment 2 of the present invention.
Fig. 4 is an optical image of ductility of the graphene aerogel-polyimide composite film according to example 3 of the present invention.
Fig. 5 shows the electrical conductivity of the graphene aerogel-polyimide composite films according to examples 1,2 and 3 of the present invention.
FIG. 6 is a schematic view of the preparation method of the present invention.
Detailed Description
Example 1: the embodiment provides a graphene aerogel-polyimide composite membrane material, and the raw materials thereof include polyimide and graphene aerogel.
Step 1: 1341.3 mg terephthalaldehyde is added into 10 ml N-methyl pyrrolidone, after complete dispersion, 11.7 mg graphene aerogel is added, and after magnetic stirring and ultrasonic treatment, complete dispersion is carried out, so that a first solution is obtained.
Step 2: 687.1 mg tris (2-aminoethyl) amine 309.5 mg diethylenetriamine is uniformly dispersed in 5ml N, N-dimethylformamide to obtain a second solution, and the second solution and the first solution are mixed uniformly and poured into a mold to form a film.
And step 3: the film is treated by adopting a gradient temperature rise mode, and the specific process comprises the following steps: 3h is placed at room temperature, and the system is changed into emulsion from solution state; then heating to 40 ℃ and preserving the temperature for 2h, so that the system is changed from emulsion to colloid; the temperature is continuously increased to 60 ℃, the temperature is kept for 12 h, then the temperature is increased to 75 ℃, the temperature is kept for 2h, finally the temperature is increased to 85 ℃, and the temperature is kept for 2h.
And 4, step 4: and carrying out hot-pressing treatment on the film, and carrying out hot pressing on the film at 100 ℃ for 5 h to obtain the graphene aerogel-polyimide composite film material.
Example 2: the embodiment provides a graphene aerogel-polyimide composite membrane material, and the raw material of the graphene aerogel-polyimide composite membrane material comprises polyimide graphene aerogel.
Step 1: 1341.3 mg terephthalaldehyde is added into 15 ml N, N-dimethylformamide, after complete dispersion, 58.4 mg graphene aerogel is added, and after magnetic stirring and ultrasonic treatment, complete dispersion is carried out, so as to obtain a first solution.
Step 2: 687.1 mg tris (2-aminoethyl) amine 309.5 mg diethylenetriamine is uniformly dispersed in 5ml of N, N-dimethylformamide to obtain a second solution, and the second solution and the first solution are uniformly mixed and then poured into a mold to form a film.
And step 3: the film is processed by adopting a gradient temperature rise mode, and the specific process is as follows: standing at room temperature for 2h, and changing the system from solution state to emulsion state; then heating to 40 ℃ and preserving the heat for 3h, wherein the system is changed into a colloid from a latex state; and continuously heating to 60 ℃, preserving heat for 10h, then heating to 80 ℃, preserving heat for 2h, and finally heating to 90 ℃, and preserving heat for 2h.
And 4, step 4: and carrying out hot pressing treatment on the film, and carrying out hot pressing for 4 hours at 95 ℃ to obtain the graphene aerogel-polyimide composite film material.
Microscopic characterization image observation is performed on the graphene aerogel-polyimide composite film provided by this embodiment, and the result is shown in fig. 1. The graphene aerogel layer is attached to the polyimide layer, and the composite material has both the conductivity of the graphene aerogel and the repairability and recoverability of the polyimide.
The repairability of the graphene aerogel-polyimide composite film prepared in this embodiment is tested, and the test includes the following steps:
and 3, carrying out heat treatment, and carrying out hot pressing at 90 ℃ for 10 mins to obtain the repaired graphene aerogel-polyimide composite membrane material.
The repair liquid is a mixed solution of 25-100 mul, and comprises an organic solvent, an amine source and a cross-linking agent, wherein the molar ratio of the amine source to the cross-linking agent is 9:14.
the graphene aerogel-polyimide composite film provided in this example was subjected to comparison before and after repair, and the result is shown in fig. 2. Fig. 2a is a photograph of two dumbbell-shaped bars of example 2, fig. 2b is a photograph of the two bars laid out after being cut off, and fig. 2c is a photograph of the two bars after being successfully repaired.
Carry out the recovery cycle test with the graphite alkene aerogel-polyimide composite membrane material that this embodiment obtained, specifically be:
cutting a membrane material sample into fragments, and putting the fragments into 10 to 80 ml of mixed recovery liquid of an amine source and a cross-linking agent, wherein the molar ratio of the amine source to the cross-linking agent is 9:14, wherein the mass of the recovered fragments is 50-2000 mg, and then the fragments are heated to 55 ℃ to be soaked in 2 h; and completely dispersing the recovered solution and the sample by using an ultrasonic method, and then transferring the sample to the room temperature for soaking 24 h. And after soaking, carrying out suction filtration treatment on the sample and the recovery liquid, collecting a filtrate (graphene aerogel powder) and a filtrate (a mixed solution of an organic solvent, an amine source and a cross-linking agent), and adding a dialdehyde compound and the graphene aerogel into the filtrate to obtain a second-generation graphene aerogel-polyimide composite membrane material. The graphene-containing aerogel is 58.4 mg, the sum of 55.2% of the mass of the added dialdehyde compound and the mass of the recovery fragments is 1341.3 mg, the sum of 16.6% of the amine source and the recovery fragments in the recovery liquid is 309.5 mg, and the sum of 25.8% of the crosslinking agent and the recovery fragments in the recovery liquid is 687.1 mg.
Example 3: the embodiment provides a graphene aerogel-polyimide composite membrane material, and the raw materials thereof include polyimide and graphene aerogel.
Step 1: 1341.3 mg terephthalaldehyde is added into 20 ml of N, N-dimethylformamide, after complete dispersion, 116.9 mg graphene aerogel is added, and after magnetic stirring and ultrasonic treatment, complete dispersion is carried out, so as to obtain a first solution.
And 2, step: 687.1 mg tri (2-aminoethyl) amine and 309.5 mg diethylenetriamine are uniformly dispersed in N, N-dimethylformamide of 5ml to obtain a second solution, and the second solution and the first solution are uniformly mixed and then poured into a mold to form a film.
And 3, step 3: the film is processed by adopting a gradient temperature rise mode, and the specific process is as follows: placing the mixture at room temperature for 2.5 h, and changing the system from a solution state to an emulsion state; then heating to 40 ℃ and preserving the heat for 2.5 h, so that the system is changed from emulsion to colloid; continuously heating to 60 ℃, and keeping the temperature to be 12 h; then raising the temperature to 75 ℃, and preserving the temperature by 2 h; finally, the temperature is raised to 90 ℃, and the temperature is kept at 2h.
And 4, step 4: and (3) carrying out hot-pressing treatment on the film, and carrying out hot pressing on the film at 80 ℃ for 4h to obtain the graphene aerogel-polyimide composite film material.
An optical image of the ductility of the graphene aerogel-polyimide composite film obtained in this example was observed, and the result is shown in fig. 4. The sample can be changed into any pattern by heating at 100 ℃ for 15 min, then changing its shape and cooling. Fig. 4 is a photograph of some examples of styles that have been changed for splines.
Performing an electrical property test on the graphene aerogel-polyimide composite films obtained in the embodiments 1,2 and 3, specifically, cutting the films obtained in the embodiments 1,2 and 3 into cuboid sample bars with the same length and width, and measuring and recording the length, width and thickness of the sample bars; coating conductive silver paste on two ends of the sample strip, and standing for natural drying of the conductive silver paste; adjusting the universal meter to a resistance test file, contacting a test probe with silver pastes at two ends of the sample strip, reading and recording; the conductivity of the splines was calculated using the spline length, width, thickness and resistance, and 5-10 samples were tested and averaged. The values obtained are shown in FIG. 5. Fig. 5 is a graph of the conductivity data of examples 1,2, and 3, and it can be seen that as the weight ratio of graphene aerogel to polyiminoampere in the composite material is increased, the conductivity is greatly improved to 156S/m.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (3)
1. Graphene aerogel-polyimide composite membrane material, its characterized in that this composite membrane material contains polyimide and graphene aerogel, and its mass ratio is 6:1-200:1;
the preparation method comprises the following steps:
step 1, adding a dialdehyde compound into N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate or dichloromethane or ethanol, completely dispersing, adding graphene aerogel, and completely dispersing after magnetic stirring and ultrasonic treatment to obtain a first solution; wherein:
the mass ratio of dialdehyde to graphene aerogel is 3:1-130:1, the concentration of solute and solvent is 30 mg/ml-150 mg/ml;
step 2, uniformly dispersing a diamine compound amine source and a triamine compound cross-linking agent in a solvent to obtain a second solution, uniformly mixing the second solution with the first solution, and pouring the mixture into a mold to form a film; wherein:
the molar ratio of diamine compound to triamine compound in the second solution is 3:5-4:5, the concentration of the solute and the solvent is 20 mg/ml-210 mg/ml; the molar ratio of dialdehyde compound to triamine compound in the mixture of the first solution and the second solution is 2:1-3:1;
step 3, processing the film in the die by adopting a gradient heating mode, which comprises the following steps:
placing 0.5-3 h at room temperature, and changing the film from a solution state to a latex state;
then heating to 40 ℃ and keeping 0.5-3 h, and changing the film from emulsion to colloid;
continuously heating to 60-65 ℃, and preserving heat for 4-12 h;
then heating to 75-80 ℃, and preserving heat for 2-4 h;
finally, heating to 85-90 ℃, and preserving heat for 2-4 h;
and 4, carrying out hot pressing treatment on the film, and carrying out hot pressing on the film at 80-100 ℃ for 1-6 h.
2. The graphene aerogel-polyimide composite film according to claim 1, wherein the diamine compound amine source comprises ethylenediamine.
3. The graphene aerogel-polyimide composite film according to claim 1, wherein the triamine compound cross-linking agent comprises tris (2-aminoethyl) amine.
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| CN113121953B (en) * | 2021-03-24 | 2022-08-12 | 云南大学 | Three-dimensional integral graphene aerogel-polyimide composite material and preparation method thereof |
| CN113583442B (en) * | 2021-08-19 | 2023-03-14 | 吉林大学 | Preparation method of self-repairing polyimide composite material with photo-thermal performance for additive manufacturing |
| CN115058049B (en) * | 2022-06-09 | 2023-05-05 | 西北工业大学深圳研究院 | Variable-gradient structure flexible aerogel, preparation method thereof and flexible pressure sensor |
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| CN107286491B (en) * | 2017-06-16 | 2020-02-07 | 青岛大学 | High-conductivity carbon nanotube/graphene aerogel/polystyrene composite material and preparation method thereof |
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