CN110627041A - Preparation method of oil-soluble graphene - Google Patents
Preparation method of oil-soluble graphene Download PDFInfo
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- CN110627041A CN110627041A CN201810647876.3A CN201810647876A CN110627041A CN 110627041 A CN110627041 A CN 110627041A CN 201810647876 A CN201810647876 A CN 201810647876A CN 110627041 A CN110627041 A CN 110627041A
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Abstract
A preparation method of oil-soluble graphene comprises the steps of dispersing graphene oxide into a solvent A, adding an ammonia reducing agent to perform partial reduction reaction at the temperature of 20-200 ℃ for 1-48 h, naturally filtering or vacuum filtering by using filter paper or a filter membrane, dispersing an obtained filter cake into a solvent B, adding a long-carbon-chain compound containing hydroxyl or amino and orthoformate, reacting for 0.1-48 h at the temperature of 20-200 ℃ in a normal-pressure container or an autoclave, and separating to obtain the oil-soluble graphene. The invention has the advantages that: the graphene product with good oil solubility is obtained by modifying the surface structure of graphene by using easily-obtained long carbon chain compounds containing hydroxyl or amino and orthoformate through a chemical method, the dispersion performance and stability of the graphene in a solvent are improved, and the method does not introduce chloride ions, is energy-saving and environment-friendly and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the field of graphene material preparation, and particularly relates to a preparation method of oil-soluble graphene.
Background
Graphene is a monoatomic layer two-dimensional carbon nanomaterial, has excellent electric conduction, heat conduction and lubrication properties, and is widely concerned in the fields of photoelectric materials, energy storage materials, lubrication and the like. Compared with non-metal nanoparticles such as graphite and carbon nanotubes, graphene has better wear-resistant and friction-reducing effects, but graphene is difficult to dissolve in common organic solvents or base oil, so that inconvenience in many applications is caused. For this reason, many studies have been made on modified graphene which is oil-soluble. Patent 201510474930.5 discloses a preparation method of oil-soluble graphene: adding more than one of borate, organic chromium complex coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, paraffin, higher fatty acid ester, higher fatty alcohol, aromatic alcohol, alkyl benzene sulfonate, alkyl alcohol sulfate, alkyl alcohol sulfonate and alkyl naphthalene sulfonate into one of solvents of xylene, ethanol, water, benzene, chloroform, toluene, carbon tetrachloride, carbon disulfide or petroleum ether, uniformly mixing, filtering, washing and drying to obtain the oil-soluble graphene powder. The modification method realizes the oil solubility of the graphene through physical adsorption, the modifier is easy to elute in an organic solvent, and the stability of the graphene is low. Patent 201610532056.0 discloses a method for screening oil-soluble graphene: graphene, base oil and a dispersing agent are mixed into a uniform solution, then the solution is placed in a wall breaking machine for processing, the processed solution is subjected to centrifugal separation to remove sediments to obtain a suspension, uniform dispersion of graphene and an oil solvent is realized, and obviously, the method only can temporarily disperse ultrafine particles in graphene into the oil solvent. Patent 201710946525.8 provides a method for preparing oil-soluble graphene quantum dots, which uses citric acid and oleylamine to prepare the oil-soluble graphene quantum dots, but the graphene quantum dots are difficult to have a graphene structure. Therefore, the chemically modified graphene is provided, and the oil solubility of the graphene is realized by introducing a longer fatty chain into the graphene structure, so that the dispersion performance of the graphene in a low-polarity solvent and a non-polar solvent (oil solvent) can be fundamentally ensured, and the chemically modified graphene has very important practical significance for the production of lubricating products and oil-soluble products.
Disclosure of Invention
The graphene oxide contains carboxyl, epoxy and hydroxyl active groups, the carboxyl is converted into amide under the action of an ammonia substance, and the epoxy group is converted into amino and hydroxyl. Therefore, the invention aims to provide a preparation method of oil-soluble graphene, which uses orthoformate as a coupling agent to realize the modification of graphene by a long carbon chain compound containing hydroxyl or amino and prepare modified graphene with good dispersion performance.
The preparation method comprises the steps of dispersing graphene oxide into a solvent A, adding an ammonia reducing agent to perform partial reduction reaction at the temperature of 20-200 ℃ for 1-48 h, naturally filtering or vacuum filtering by using filter paper or a filter membrane, dispersing the obtained filter cake into a solvent B, adding a long-carbon-chain compound containing hydroxyl or amino and orthoformate, reacting for 0.1-48 h at the temperature of room temperature-200 ℃ in a normal-pressure container or an autoclave, and separating to obtain the oil-soluble graphene.
The preparation method of the present invention is characterized in that the dispersion method of the graphene oxide in the solvent may be mechanical stirring, ultrasonic dispersion, or a combination of both.
The preparation method is characterized in that the solvent A is one of or a mixed solvent of dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, benzene, toluene, xylene, nitrobenzene, dibutyl ether, diphenyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ether, triethylene glycol ether, ethylene glycol, 1-10 carbon alcohol, N-dimethylformamide, N-dimethylacetamide. Tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, 1-10 carbon alcohol or a mixed solvent thereof is preferable. The using amount of the solvent is 50-10000 times, preferably 500-1500 times of the mass of the graphene oxide.
The preparation method is characterized in that the ammonia reducing agent is ammonia water, ammonium acetate, ammonium carbonate, ammonium sulfate, ammonium nitrate or ammonium chloride; the adding amount of the ammonia reducing agent is 0.01-20 times, preferably 0.1-1.5 times of the mass of the graphene oxide.
The preparation method is characterized in that the reduction reaction can be carried out in a normal-pressure container or a high-pressure reaction kettle, carboxyl in graphene is amidated, an epoxy structure is changed into amino and hydroxyl, and the hydroxyl is reserved under the reduction condition and can be confirmed from the infrared spectrum characteristics of the product.
The preparation method of the invention is characterized in that the dispersing method for dispersing the filter cake into the solvent B can be mechanical stirring, ultrasonic dispersing or the combination of the two.
The preparation method is characterized in that the solvent B is one of or a mixed solvent of diphenyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, tetrahydrofuran, benzene, toluene, xylene and nitrobenzene. Preferred are phenyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solvent thereof. The using amount of the solvent is 50-10000 times, preferably 500-1500 times of the mass of the graphene oxide.
The preparation method is characterized in that the long carbon chain compound containing hydroxyl or amino is primary alcohol and secondary alcohol with the carbon number of 4-38, primary amine and secondary amine with the carbon number of 4-38, or alcohol or amine compound with longer carbon chain obtained by chemical synthesis, such as forty-carbon alcohol and forty-alkyl amine, preferably dodecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, triacontanol, dotriacontanol, dodecylamine, hexadecylamine, octadecylamine, dioctadecylamine and icosenamine. The addition amount of the long carbon chain compound is 0.01-10 times, preferably 0.5-2 times of the mass of the graphene oxide.
The preparation method is characterized in that the orthoformate is trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate and tripentyl orthoformate, and preferably trimethyl orthoformate and triethyl orthoformate.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the oil-soluble graphene, disclosed by the invention, a long-carbon-chain alcohol or amine compound is utilized to react with functional groups on orthoformate and graphene oxide, the surface structure of the graphene is modified in one step, a graphene product with good oil solubility can be efficiently obtained, one carbon in the orthoformate is added between a long alkyl chain and the partially reduced graphene oxide and is connected with the long alkyl chain through a chemical bond, the stability of a molecular structure is ensured, and the service performance is improved;
(2) the preparation method of the oil-soluble graphene has a short route, is easy to implement, and can be used for producing oil-soluble graphene products in a large scale.
(3) The method has the advantages of small raw material consumption, high atom economic benefit and small discharge amount of waste pollutants.
(4) The product prepared by the invention has more excellent dispersion performance, and can be better applied to the fields of photoelectric materials, energy storage materials and oil-based lubricating materials.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
A preparation method of oil-soluble graphene, comprising the following steps:
utilizing ultrasonic wave to assist dispersion, preparing 40mL of 0.4mg/mL graphene oxide tetrahydrofuran solution, adding 0.56g of ammonia water under stirring, ultrasonically mixing for 10min at room temperature, heating to 68 ℃ under mechanical stirring for reflux reaction for 4h, filtering with a 0.5-micrometer filter membrane, dispersing a filter cake into 20mL of N, N-dimethylformamide under the ultrasonic action, adding 0.52g of triethyl orthoformate and 0.80g of dodecanol, heating to 140 ℃ under stirring for reaction for 5h, filtering with a 0.22-micrometer filter membrane after reaction, washing with 5mL of deionized water for 1 time, and vacuum drying at 60 ℃ for 4h to obtain the oil-soluble graphene.
Structural characterization: infrared Spectrum (FT-IR) at 2926cm-1And 2849cm-1Shows a characteristic peak of methylene, and the proto-graphene oxide is at 1726cm-1The carbonyl peak of (2) was transferred to 1574cm-1Here, the formation of a new bond is illustrated, with successful incorporation of dodecanol on graphene.
Dispersing performance: the concentration value of the obtained oil-soluble graphene in toluene is 1.19mg/mL, and the stability of the dispersion liquid is more than 6 months; the dispersion concentration in the base oil is 0.96mg/mL, and the stability of the dispersion is more than 6 months.
Example 2:
a preparation method of oil-soluble graphene, comprising the following steps:
utilizing ultrasonic wave to assist dispersion, preparing 30mL of 0.4mg/mL oxidized graphene ethylene glycol diethyl ether solution, adding 0.8g of ammonium chloride under stirring, reacting for 6h at 80 ℃, carrying out vacuum filtration by using a fine-pore filter paper, dispersing a filter cake into 15mL of N-methyl pyrrolidone, adding 0.6g of trimethyl orthoformate and 0.85g of hexadecylamine, uniformly stirring, transferring into a hydrothermal reaction kettle, sealing, heating to 180 ℃ for reaction for 4h, cooling, taking out, filtering by using a 0.22 mu m filter membrane, washing by using 5mL of absolute ethyl alcohol, and carrying out vacuum drying for 3h at 80 ℃ to obtain the oil-soluble graphene.
Structural characterization: infrared Spectrum (FT-IR) at 2922cm-1And 2845cm-1Shows a characteristic peak of methylene, and the proto-graphene oxide is at 1726cm-1The carbonyl peak of (A) disappears at 1030cm-1The C — O absorption of (a) was changed, indicating successful incorporation of hexadecylamine on graphene.
Dispersing performance: the maximum dispersion concentration of the obtained oil-soluble graphene in toluene is 1.11mg/mL, and the stability of the dispersion liquid is more than 6 months.
Example 3:
a preparation method of oil-soluble graphene, comprising the following steps:
preparing 40mL of 0.5mg/mL graphene oxide N, N-dimethylformamide solution by utilizing ultrasonic-assisted dispersion, adding 0.6g of ammonium carbonate while stirring, reacting for 2.5h at 120 ℃, performing vacuum filtration by using a 0.22-micron filter membrane, dispersing a filter cake into 30mL diphenyl ether, adding 0.8g of trimethyl orthoformate and 1.0g of eicosanol, transferring into a high-pressure reaction kettle, heating to 160 ℃, reacting for 6h, cooling, filtering by using the 0.1-micron filter membrane, washing for 1 time by using 2mL of absolute ethyl alcohol, and performing vacuum drying for 4h at 80 ℃ to obtain the oil-soluble graphene.
Structural characterization: infrared Spectrum (FT-IR) at 2926cm-1And 2850cm-1Shows a characteristic peak of methylene, and the proto-graphene oxide is at 1726cm-1The carbonyl peak of (A) was transferred to 1669cm-1At 1030cm-1The nearby C — O absorption changes, indicating successful incorporation of dodecylamine onto graphene.
Dispersing performance: the concentration value of the obtained oil-soluble graphene in toluene is 1.02 mg/mL; the stability of the obtained graphene dispersion liquid is more than 6 months.
Examples 4 to 8
A preparation method of oil-soluble graphene, comprising the following steps:
preparing 100mL of graphene oxide n-propanol solution of 0.50mg/mL by using ultrasonic-assisted dispersion, adding 0.8g of ammonia water under stirring, reacting for 4 hours at 100 ℃, performing vacuum filtration by using a fine-pore filter paper, dividing a filter cake into 5 parts, dispersing into 20mL of sulfolane, adding 0.5g of triethyl orthoformate, adding 0.32g of octanol, 0.4g of decanol, 0.5g of tetradecanol, 0.56g of hexadecanol and 0.6g of octadecanol respectively, stirring uniformly, transferring into a hydrothermal reaction kettle, purging air by using nitrogen, sealing, heating to 170 ℃ for reacting for 4 hours, cooling, taking out, filtering by using a filter membrane of 0.22 mu m, washing for 2 times by using 5mL of absolute ethyl alcohol, and drying for 3 hours at 70 ℃ in vacuum to obtain the oil-soluble graphene modified by octanol, decanol, tetradecanol, hexadecanol and octadecanol respectively.
Structural characterization: in the infrared spectrum (FT-IR), the five products were all at 2920-2840cm-1Shows a characteristic peak of methylene at 1050cm-1The C — O absorption changes from side to side, indicating that these alcohols have been successfully bound to graphene.
Dispersing performance: the dispersion concentrations of the obtained octanol, decanol, tetradecanol, hexadecanol and octadecanol modified oil-soluble graphene in toluene are respectively 1.05mg/mL, 1.1mg/mL, 1.15mg/mL, 1.25mg/mL and 1.28mg/mL, and the stability of each dispersion is more than 6 months.
Example 9:
a preparation method of oil-soluble graphene, comprising the following steps:
preparing 20mL of 0.60mg/mL graphene oxide ethanol solution, adding 1.0g of ammonium carbonate while stirring, performing reflux reaction for 6 hours, performing vacuum filtration by using a fine-pore filter paper, dispersing a filter cake into 20mL nitrobenzene, adding 0.8g of triethyl orthoformate and 1.2g of tetracosanol, uniformly stirring, transferring into a hydrothermal reaction kettle, exhausting air by using nitrogen, sealing, heating to 130 ℃, reacting for 6 hours, cooling, taking out, filtering by using a 0.22-micrometer filter membrane, washing for 2 times by using 5mL of absolute ethyl alcohol each time, and performing vacuum drying for 4 hours at 70 ℃ to obtain the oil-soluble graphene.
Structural characterization: infrared Spectrum (FT-IR) at 2923cm-1And 2851cm-1Shows a characteristic peak of methylene, and the proto-graphene oxide is at 1726cm-1The carbonyl peak of (A) disappears at 1030cm-1The C-O absorption of (a) changed, indicating successful binding of tetracosanol to graphene.
Dispersing performance: the dispersion concentration value of the obtained oil-soluble graphene in oil is 1.40mg/mL, and the stability of the dispersion liquid is more than 6 months.
Claims (9)
1. The preparation method of the oil-soluble graphene is characterized by comprising the steps of dispersing graphene oxide into a solvent A, adding an ammonia reducing agent to perform partial reduction reaction at the temperature of 20-200 ℃ for 1-48 h, naturally filtering or vacuum filtering by using filter paper or a filter membrane, dispersing an obtained filter cake into a solvent B, adding a long-carbon-chain compound containing hydroxyl or amino and orthoformate, reacting for 0.1-48 h at the temperature of 20-200 ℃ in a normal-pressure container or an autoclave, and separating to obtain the oil-soluble graphene.
2. The method according to claim 1, wherein the graphene oxide is dispersed in the solvent by mechanical stirring, ultrasonic dispersion, or a combination thereof.
3. The method according to claim 1, wherein the solvent A is one or a mixture of two solvents selected from the group consisting of dimethylsulfoxide, sulfolane, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, benzene, toluene, xylene, nitrobenzene, dibutyl ether, diphenyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ether, triethylene glycol ether, ethylene glycol, alcohols of 1 to 10 carbon atoms, N-dimethylformamide, N-dimethylacetamide, preferably tetrahydrofuran, N-dimethylformamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, alcohols of 1 to 10 carbon atoms, and a mixture of two solvents, the using amount of the solvent is 50-10000 times, preferably 500-1500 times of the mass of the graphene oxide.
4. The method according to claim 1, wherein the ammonia-based reducing agent is ammonia water, ammonium acetate, ammonium carbonate, ammonium sulfate, ammonium nitrate, ammonium chloride; the adding amount of the ammonia reducing agent is 0.01-20 times, preferably 0.1-1.5 times of the mass of the graphene oxide.
5. The method according to claim 1, wherein the reduction is carried out in an atmospheric pressure vessel or in an autoclave.
6. The process of claim 1, wherein the dispersing of the filter cake into the solvent B is carried out by mechanical stirring, ultrasonic dispersing or a combination thereof.
7. The preparation method according to claim 1, wherein the solvent B is one or a mixture of diphenyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, tetrahydrofuran, benzene, toluene, xylene and nitrobenzene, and is preferably phenyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or a mixture thereof, and the amount of the solvent is 50 to 10000 times, preferably 500 to 1500 times, the mass of the graphene oxide.
8. The method according to claim 1, wherein the long carbon chain compound containing hydroxyl or amino groups is a primary or secondary alcohol having 4 to 38 carbon atoms, a primary or secondary amine having 4 to 38 carbon atoms, or a longer carbon chain alcohol or amine compound obtained by chemical synthesis, such as forty-carbon alcohol, forty-alkyl amine, preferably dodecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, triacontanol, dotriacontanol, dodecylamine, hexadecylamine, octadecylamine, dioctadecylamine, eicosylamine, and the amount of the long carbon chain compound added is 0.01 to 10 times, preferably 0.5 to 2 times, the mass of graphene oxide.
9. The method according to claim 1, wherein the orthoformate is trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tripentyl orthoformate, preferably trimethyl orthoformate, triethyl orthoformate.
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| CN111205904A (en) * | 2020-01-22 | 2020-05-29 | 上海应用技术大学 | Lubricating property reinforcing agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722352A (en) * | 2017-11-06 | 2018-02-23 | 浙江山峪科技股份有限公司 | A kind of chain alkyl amino-functionalization graphene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107722352A (en) * | 2017-11-06 | 2018-02-23 | 浙江山峪科技股份有限公司 | A kind of chain alkyl amino-functionalization graphene and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111205904A (en) * | 2020-01-22 | 2020-05-29 | 上海应用技术大学 | Lubricating property reinforcing agent and preparation method and application thereof |
| CN111205904B (en) * | 2020-01-22 | 2022-10-14 | 上海应用技术大学 | Lubricating property reinforcing agent and preparation method and application thereof |
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Application publication date: 20191231 |