CN111453717A - Efficient heat-resistant graphene film and preparation method thereof - Google Patents

Efficient heat-resistant graphene film and preparation method thereof Download PDF

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CN111453717A
CN111453717A CN202010525089.9A CN202010525089A CN111453717A CN 111453717 A CN111453717 A CN 111453717A CN 202010525089 A CN202010525089 A CN 202010525089A CN 111453717 A CN111453717 A CN 111453717A
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parts
stirring
graphene
temperature
resistant
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王凯
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    • 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
    • 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
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character

Abstract

The invention discloses a high-efficiency heat-resistant graphene film and a preparation method thereof, wherein the film is prepared from the following raw materials in parts by weight: the material comprises, by weight, 5-7 parts of bisphenol A, 30-40 parts of thionyl chloride, 100-110 parts of graphene, 10-14 parts of ricinoleic acid, 8-10 parts of pentaerythritol, 1-2 parts of stearate and 40-50 parts of modified sol solution. The graphene film disclosed by the invention is good in composite property, high in uniformity and stability and excellent in comprehensive performance, is particularly suitable for being used as an integrated circuit film, and has high-temperature-resistant stability.

Description

Efficient heat-resistant graphene film and preparation method thereof
Technical Field
The invention belongs to the field of films, and particularly relates to a high-efficiency heat-resistant graphene film and a preparation method thereof.
Background
Graphene is considered to be one of the best materials for manufacturing a film material due to its superior thermal stability, chemical stability, mechanical stability, high light transmittance and electron mobility. The graphene film has a wide application range in the fields of electronics, photons and photoelectric equipment, has a great development prospect, and the current preparation methods of the graphene film comprise a spin-coating method, a spraying method, a self-assembly method and a vapor deposition method, but the methods have the defects of poor uniformity, complex process, low raw material utilization rate and the like, and particularly for the graphene film for an integrated circuit, the graphene film is required to have high thermal stability;
the comparison document CN201810759152.8 discloses a heat-resistant graphene film and a preparation method thereof, wherein an aluminum dihydrogen phosphate aqueous solution is used as a reaction solvent, pyromellitic dianhydride is used as a monomer, polymerization is carried out under the action of sodium persulfate to obtain aluminum dihydrogen phosphate-doped polyanhydride, then the polyanhydride is used for treating polyphenyl ether and is dispersed into chloroform, and then the polyphenyl ether is blended with diphenyl silanediol and graphene oxide, and high-temperature esterification is carried out to realize the dispersion compatibility of graphene among polyphenyl ethers; it can be seen that it is a graphene-doped polyphenylene ether film, which is a process plastic, and inevitably reduces the electrical properties of the finished product, and the surface strength is far from comparable to that of a pure graphene film.
Disclosure of Invention
The invention aims to provide a high-efficiency heat-resistant graphene film and a preparation method thereof, aiming at the defects and shortcomings of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-efficiency heat-resistant graphene film is composed of the following raw materials in parts by weight:
the material comprises, by weight, 5-7 parts of bisphenol A, 30-40 parts of thionyl chloride, 100-110 parts of graphene, 10-14 parts of ricinoleic acid, 8-10 parts of pentaerythritol, 1-2 parts of stearate and 40-50 parts of modified sol solution.
The stearate is one of barium stearate and calcium stearate.
The modified sol solution is prepared from the following raw materials in parts by weight:
60-70 parts of tetrabutyl titanate, 90-100 parts of toluene, 10-13 parts of hydrogen peroxide, 0.7-2 parts of calcium ricinoleate and 1-2 parts of coconut diethanolamide.
The concentration of the hydrogen peroxide is 4.5-6%.
The preparation method of the modified sol solution comprises the following steps:
(1) adding coconut diethanolamide into toluene, stirring, adding calcium ricinoleate, heating to 50-55 deg.C, stirring for 10-20 min to obtain toluene emulsion;
(2) adding tetrabutyl titanate into deionized water with the weight of 40-50 times of that of the tetrabutyl titanate, uniformly stirring, adding the toluene emulsion, stirring for 3-4 hours, raising the temperature to 65-70 ℃, dropwise adding hydrogen peroxide, and stirring for 10-20 minutes under heat preservation to obtain the modified sol solution.
The preparation method of the high-efficiency heat-resistant graphene film comprises the following steps:
(1) adding ricinoleic acid into thionyl chloride, stirring uniformly, adding graphene, raising the temperature to 55-60 ℃, keeping the temperature and stirring for 1-2 hours, and distilling to remove the thionyl chloride to obtain acidified graphene;
(2) adding pentaerythritol into the modified sol solution, uniformly stirring, mixing with the acidified graphene, raising the temperature to 40-50 ℃, keeping the temperature and stirring for 15-20 hours, discharging, adding bisphenol A, raising the temperature to 70-80 ℃, keeping the temperature and stirring for 100-130 minutes, performing suction filtration, washing the precipitate with dimethylformamide, drying at the temperature of 50-60 ℃ for 5-7 hours in vacuum, and cooling to normal temperature to obtain heat-resistant modified graphene;
(3) mixing the heat-resistant modified graphene with stearate, adding the mixture into dimethylformamide 13-20 times the weight of the mixture, carrying out heat preservation and stirring at 85-90 ℃ for 140 minutes, uniformly coating the mixture on a glass plate, sending the glass plate into an oven, drying at 70-75 ℃ for 10-13 hours, discharging, cooling, and stripping the film to obtain the high-efficiency heat-resistant graphene film.
The invention has the advantages that:
according to the invention, tetrabutyl titanate is used as a precursor, and hydrolysis and deposition are carried out in an acidified graphene aqueous solution, so that not only is the deposition and compounding of sol on the surface of graphene effectively promoted, but also the heat-resistant stability of the composite material is improved through the modification of a bisphenol A esterification material.
Detailed Description
Example 1
A high-efficiency heat-resistant graphene film is composed of the following raw materials in parts by weight:
bisphenol A7, thionyl chloride 40, graphene 110, ricinoleic acid 14, pentaerythritol 10, stearate 2 and a modified sol solution 50.
The stearate is barium stearate.
The modified sol solution is prepared from the following raw materials in parts by weight:
tetrabutyl titanate 70, toluene 100, hydrogen peroxide 13, calcium ricinoleate 2 and coconut diethanolamide 2.
The concentration of the hydrogen peroxide is 6%.
The preparation method of the modified sol solution comprises the following steps:
(1) adding coconut diethanolamide into toluene, stirring, adding calcium ricinoleate, raising the temperature to 55 ℃, and stirring for 20 minutes under the condition of heat preservation to obtain toluene emulsion;
(2) adding tetrabutyl titanate into deionized water with the weight 50 times of that of the tetrabutyl titanate, uniformly stirring, adding the toluene emulsion, stirring for 4 hours, raising the temperature to 70 ℃, dropwise adding hydrogen peroxide, and stirring for 20 minutes under the condition of heat preservation to obtain the modified sol solution.
The preparation method of the high-efficiency heat-resistant graphene film comprises the following steps:
(1) adding ricinoleic acid into thionyl chloride, stirring uniformly, adding graphene, raising the temperature to 60 ℃, keeping the temperature and stirring for 2 hours, and distilling to remove the thionyl chloride to obtain acidified graphene;
(2) adding pentaerythritol into the modified sol solution, uniformly stirring, mixing with the acidified graphene, raising the temperature to 50 ℃, keeping the temperature and stirring for 20 hours, discharging, adding bisphenol A, raising the temperature to 80 ℃, keeping the temperature and stirring for 130 minutes, performing suction filtration, washing the precipitate with dimethylformamide, drying at the temperature of 60 ℃ in vacuum for 7 hours, and cooling to normal temperature to obtain heat-resistant modified graphene;
(3) and mixing the heat-resistant modified graphene with stearate, adding the mixture into dimethylformamide with the weight being 20 times that of the mixture, preserving heat and stirring for 140 minutes at 90 ℃, uniformly coating the mixture on a glass plate, sending the glass plate into an oven, drying the glass plate for 13 hours at 75 ℃, discharging the material, cooling, and stripping the film to obtain the high-efficiency heat-resistant graphene film.
Example 2
A high-efficiency heat-resistant graphene film is composed of the following raw materials in parts by weight:
bisphenol A5, thionyl chloride 30, graphene 100, ricinoleic acid 10, pentaerythritol 8, stearate 1 and a modified sol solution 40.
The stearate is calcium stearate.
The modified sol solution is prepared from the following raw materials in parts by weight:
tetrabutyl titanate 60, toluene 90, hydrogen peroxide 10, calcium ricinoleate 0.7 and coconut diethanolamide 1.
The concentration of the hydrogen peroxide is 4.5%.
The preparation method of the modified sol solution comprises the following steps:
(1) adding coconut diethanolamide into toluene, stirring, adding calcium ricinoleate, heating to 50 deg.C, and stirring for 10 min to obtain toluene emulsion;
(2) adding tetrabutyl titanate into deionized water 40 times of the weight of tetrabutyl titanate, uniformly stirring, adding the toluene emulsion, stirring for 3 hours, raising the temperature to 65 ℃, dropwise adding hydrogen peroxide, and stirring for 10 minutes under heat preservation to obtain the modified sol solution.
The preparation method of the high-efficiency heat-resistant graphene film comprises the following steps:
(1) adding ricinoleic acid into thionyl chloride, stirring uniformly, adding graphene, raising the temperature to 55 ℃, keeping the temperature and stirring for 1 hour, and distilling to remove the thionyl chloride to obtain acidified graphene;
(2) adding pentaerythritol into the modified sol solution, uniformly stirring, mixing with the acidified graphene, raising the temperature to 40 ℃, keeping the temperature and stirring for 15 hours, discharging, adding bisphenol A, raising the temperature to 70 ℃, keeping the temperature and stirring for 100 minutes, performing suction filtration, washing the precipitate with dimethylformamide, drying at the temperature of 50 ℃ for 5 hours in vacuum, and cooling to normal temperature to obtain heat-resistant modified graphene;
(3) and mixing the heat-resistant modified graphene with stearate, adding the mixture into dimethylformamide 13 times the weight of the mixture, preserving heat and stirring for 100 minutes at 85 ℃, uniformly coating the mixture on a glass plate, sending the glass plate into an oven, drying the glass plate for 10 hours at 70 ℃, discharging, cooling, and stripping the film to obtain the high-efficiency heat-resistant graphene film.
Comparative example 1
A high-efficiency heat-resistant graphene film is composed of the following raw materials in parts by weight:
bisphenol A7, thionyl chloride 40, graphene 110, ricinoleic acid 14, pentaerythritol 10, barium stearate 2.
The preparation method of the high-efficiency heat-resistant graphene film comprises the following steps:
(1) adding ricinoleic acid into thionyl chloride, stirring uniformly, adding graphene, raising the temperature to 60 ℃, keeping the temperature and stirring for 2 hours, and distilling to remove the thionyl chloride to obtain acidified graphene;
(2) mixing pentaerythritol with the acidified graphene, raising the temperature to 50 ℃, preserving heat and stirring for 20 hours, discharging, adding bisphenol A, raising the temperature to 80 ℃, preserving heat and stirring for 130 minutes, performing suction filtration, washing a precipitate with dimethylformamide, drying at the temperature of 60 ℃ in vacuum for 7 hours, and cooling to normal temperature to obtain modified graphene;
(3) and mixing the modified graphene with barium stearate, adding the mixture into dimethylformamide with the weight being 20 times that of the mixture, preserving heat and stirring the mixture for 140 minutes at 90 ℃, uniformly coating the mixture on a glass plate, sending the glass plate into an oven, drying the glass plate for 13 hours at 75 ℃, discharging the material, cooling the material, and stripping the film to obtain the graphene film.
Comparative example 2
A high-efficiency heat-resistant graphene film is composed of the following raw materials in parts by weight:
bisphenol A5, thionyl chloride 30, graphene 100, ricinoleic acid 10, pentaerythritol 8, calcium stearate 1 and a modified sol solution 40.
The preparation method of the high-efficiency heat-resistant graphene film comprises the following steps:
(1) adding ricinoleic acid into thionyl chloride, stirring uniformly, adding graphene, raising the temperature to 55 ℃, keeping the temperature and stirring for 1 hour, and distilling to remove the thionyl chloride to obtain acidified graphene;
(2) mixing pentaerythritol with the acidified graphene, raising the temperature to 40 ℃, keeping the temperature and stirring for 15 hours, discharging, adding bisphenol A, raising the temperature to 70 ℃, keeping the temperature and stirring for 100 minutes, performing suction filtration, washing a precipitate with dimethylformamide, drying the precipitate at the temperature of 50 ℃ in vacuum for 5 hours, and cooling to the normal temperature to obtain modified graphene;
(3) and mixing the heat-resistant modified graphene with calcium stearate, adding the mixture into dimethylformamide 13 times the weight of the mixture, preserving heat and stirring for 100 minutes at 85 ℃, uniformly coating the mixture on a glass plate, sending the glass plate into an oven, drying the glass plate for 10 hours at 70 ℃, discharging, cooling, and stripping the film to obtain the graphene film.
And (3) performance testing:
Figure 665580DEST_PATH_IMAGE002

Claims (6)

1. the efficient heat-resistant graphene film is characterized by being prepared from the following raw materials in parts by weight:
the material comprises, by weight, 5-7 parts of bisphenol A, 30-40 parts of thionyl chloride, 100-110 parts of graphene, 10-14 parts of ricinoleic acid, 8-10 parts of pentaerythritol, 1-2 parts of stearate and 40-50 parts of modified sol solution.
2. The graphene film as claimed in claim 1, wherein the stearate is one of barium stearate and calcium stearate.
3. The efficient heat-resistant graphene film according to claim 1, wherein the modified sol solution is prepared from the following raw materials in parts by weight:
60-70 parts of tetrabutyl titanate, 90-100 parts of toluene, 10-13 parts of hydrogen peroxide, 0.7-2 parts of calcium ricinoleate and 1-2 parts of coconut diethanolamide.
4. The efficient heat-resistant graphene film according to claim 3, wherein the concentration of hydrogen peroxide is 4.5-6%.
5. The efficient heat-resistant graphene film according to claim 3, wherein the preparation method of the modified sol solution comprises the following steps:
(1) adding coconut diethanolamide into toluene, stirring, adding calcium ricinoleate, heating to 50-55 deg.C, stirring for 10-20 min to obtain toluene emulsion;
(2) adding tetrabutyl titanate into deionized water with the weight of 40-50 times of that of the tetrabutyl titanate, uniformly stirring, adding the toluene emulsion, stirring for 3-4 hours, raising the temperature to 65-70 ℃, dropwise adding hydrogen peroxide, and stirring for 10-20 minutes under heat preservation to obtain the modified sol solution.
6. The preparation method of the high-efficiency heat-resistant graphene film according to claim 1, characterized by comprising the following steps:
(1) adding ricinoleic acid into thionyl chloride, stirring uniformly, adding graphene, raising the temperature to 55-60 ℃, keeping the temperature and stirring for 1-2 hours, and distilling to remove the thionyl chloride to obtain acidified graphene;
(2) adding pentaerythritol into the modified sol solution, uniformly stirring, mixing with the acidified graphene, raising the temperature to 40-50 ℃, keeping the temperature and stirring for 15-20 hours, discharging, adding bisphenol A, raising the temperature to 70-80 ℃, keeping the temperature and stirring for 100-130 minutes, performing suction filtration, washing the precipitate with dimethylformamide, drying at the temperature of 50-60 ℃ for 5-7 hours in vacuum, and cooling to normal temperature to obtain heat-resistant modified graphene;
(3) mixing the heat-resistant modified graphene with stearate, adding the mixture into dimethylformamide 13-20 times the weight of the mixture, carrying out heat preservation and stirring at 85-90 ℃ for 140 minutes, uniformly coating the mixture on a glass plate, sending the glass plate into an oven, drying at 70-75 ℃ for 10-13 hours, discharging, cooling, and stripping the film to obtain the high-efficiency heat-resistant graphene film.
CN202010525089.9A 2020-06-10 2020-06-10 Efficient heat-resistant graphene film and preparation method thereof Withdrawn CN111453717A (en)

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Application Number Priority Date Filing Date Title
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Application publication date: 20200728