CN110627052A - Preparation method of water-soluble graphene - Google Patents
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Abstract
A preparation method of water-soluble graphene comprises the steps of dispersing graphene oxide into a solvent, adding an ammonia reducing agent for partial reduction reaction, filtering, dispersing a filter cake into the solvent, adding a water-soluble micromolecule compound containing hydroxyl or amino and orthoformate, heating for reaction, and separating to obtain the graphene with excellent dispersibility in water. The invention has the advantages that: the graphene product with good dispersibility in water is obtained by utilizing the cheap and easily-obtained micromolecular compound containing hydroxyl or amino and the orthoformate modified graphene surface structure, 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 water-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, water-soluble graphene has better dispersion stability and wear-resistant and friction-reducing effects, and can not only reduce friction due to relative sliding between contact surfaces, but also form a thin film at high temperature and high pressure, so that direct contact between the friction surfaces is avoided, and the bearing capacity is improved [ Applied Physics a-Materials Science & Processing, 2011 (105): 827-832.].
However, graphene is difficult to be dissolved in water and common organic solvents, so that the preparation process of various materials is difficult and the material performance is poor. For this reason, many studies have been made on modified graphene having water solubility. Patent 201410336551.5 discloses a preparation method of water-soluble graphene: oxidizing natural crystalline flake graphite into graphene oxide, reacting the graphene oxide with thionyl chloride to obtain graphene with acyl chloride groups on the surface, and sequentially carrying out nucleophilic substitution reaction on the graphene oxide with 1, 3-propane diamine, cyanuric chloride and a diol compound to obtain water-soluble graphene with hydroxyl groups on the surface, wherein the content of the hydroxyl groups is 0.005-0.02%. The obtained modified graphene has good water solubility, can be conveniently mixed with other concrete preparation materials and uniformly dispersed, and is used for preparing reinforced and toughened concrete products. Patent 201110260278.9 discloses an improved water-soluble graphene of L-cysteine hydrochloride, combined with nano noble metals into a composite material. Patent 201110044749.2 discloses a Coomassie brilliant blue modified water-soluble graphene, the solubility of which can reach 1-1.5 mg/mL, and the conductivity of which can reach 1-2 S.m-1Can stably exist for 3-6 months without precipitation. Patent 201110412306.4 discloses a water-soluble graphene for supercapacitor electrode materials and a preparation method thereof, the components of the water-soluble graphene comprise graphite oxide, 1-ethyl (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine, ethylenediamine, acrylic acid, sodium p-styrenesulfonate, an initiator and a reducing agent, the graphene is grafted with a large amount of negative charges on the surface, the graphene can be well dissolved in water by the principle of negative charge repulsion, the electrochemical performance of a graphene-based capacitor is improved, and the graphene-based capacitor has a wider application prospect in the fields of supercapacitors, solar cells and the like. Patent 201410696906.1 discloses a method for preparing water-soluble graphene, which comprises adding graphene, dihydroxybenzaldehyde and methylamino acetic acid into DMF, performing ultrasonic dispersion uniformly, stirring and refluxing in an oil bath at 110-130 ℃, centrifuging while hot, repeatedly washing with absolute ethanol, drying to obtain an organic matter-modified aminated graphene, and reacting with gamma-glycidyl ether oxypropyltrimethylsilane (KH560) in ethanol at room temperatureThe epoxy group grafted graphene is obtained after 15-24 h, and finally, the sulfonated graphene is obtained through reaction with sulfanilic acid, so that the aggregation phenomenon of the graphene in an aqueous solution is effectively prevented, the water solubility of the graphene is improved, and the method is environment-friendly and pollution-free. Patent 201310296390.7 discloses a method for preparing p-hydrazino benzenesulfonic acid modified water-soluble graphene, wherein the obtained water-soluble graphene has basic structural characteristics similar to those of graphene, has good solubility, and is expected to be used as a novel material or a composite component for preparing related composite materials in the aspects of ductile electrodes, supercapacitors, hydrogen storage, solar cells, thin film transistors and the like. Patent 201410490875.4 discloses a method for preparing graphene using guanidine hydrochloride as a reducing agent, wherein a soluble high molecular polymer and guanidine hydrochloride are added into graphene oxide to obtain water-soluble graphene. Most of the researches adopt the traditional chemical method, the production efficiency is very low, particularly, the method of using the halogenating reagent as mentioned in patent 201410336551.5 changes the carboxyl in the graphene oxide into acyl chloride, the dosage of the toxic reagent is large, the separation is difficult and the pollution is serious, and the development of the simple, efficient and environment-friendly preparation technology has very important practical significance.
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 water-soluble graphene, which uses orthoformate as a coupling agent to realize the modification of water-soluble micromolecular compounds containing hydroxyl or amino on graphene, does not contain chloride ions which are difficult to remove, reduces the emission of pollutants from the source, and realizes the simple, efficient and environment-friendly preparation of the modified graphene with good water dispersibility.
The preparation method comprises the steps of dispersing graphene oxide into a solvent A, adding an ammonia reducing agent for partial reduction reaction, filtering, dispersing a filter cake into a solvent B, adding a water-soluble micromolecule compound containing hydroxyl or amino and orthoformate, reacting under a certain condition, and separating to obtain the water-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 or a mixed solvent of dibutyl 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, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, benzene, toluene, xylene, nitrobenzene and water, preferably tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, 1-10 carbon alcohol or a mixed solvent thereof, and the using amount of the solvent is 50-10000 times, preferably 500-1500 times of the mass of 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, the reaction is carried out under the conditions that the reaction temperature is controlled to be 20-200 ℃ and the reaction time is controlled to be 1-48 h, carboxyl in graphene is amidated, an epoxy structure is changed into amino and hydroxyl, and under the reduction condition, the hydroxyl is reserved, and the infrared spectrum characteristics of the product can be verified.
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 acetonitrile, 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 or a mixed solvent thereof, preferably tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone or a mixed solvent thereof, and the using amount of the solvent is 50-10000 times, preferably 500-1500 times of the mass of graphene oxide.
The preparation method is characterized in that the water-soluble micromolecule compound containing hydroxyl or amino is ethanolamine, diethanolamine, triethanolamine, aminopropanol, aminobutanol, aminopentanol, aminohexanol, 2-amino-1, 3-propanediol, 3-amino-1, 2-propanediol, aminobutanediol, trimethylolaminomethane, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, butanetetraol, pentaerythritol, xylitol, sorbitol, mannitol, vitamin C, chitosan, fructose, glucose, dextran, maltose and hyaluronic acid; natural amino acids such as lysine, tryptophan, threonine, serine, phenylalanine, and arginine; aminoalkyl acids such as glycine, aminopropionic acid, aminobutyric acid, and aminopentanoic acid; aminoalkylsulfonic acids such as aminomethanesulfonic acid, aminoethanesulfonic acid, and aminopropanesulfonic acid; aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, hydroxybenzenesulfonic acid, hydroxyalkylsulfonic acid; dialkylamines such as ethylenediamine, propylenediamine, and butylenediamine; diethylenetriamine, triethylene tetramine, tetraethylenepentamine and pentaethylenehexamine. The addition amount of the water-soluble small molecular compound is 0.1-10 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.
The preparation method is characterized in that the reaction can be carried out in a normal-pressure container or an autoclave under certain conditions, the reaction temperature is between room temperature and 200 ℃, the reaction time is 0.1 to 48 hours, and the reaction time is preferably 4 to 10 hours at 80 to 200 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the water-soluble graphene, a graphene product with good water solubility can be efficiently obtained by utilizing the cheap and easily-obtained hydroxyl or amino-containing micromolecular compound and the orthoformate modified graphene surface structure, one carbon in the orthoformate is added between the water-soluble micromolecule and the partially reduced graphene oxide and is connected by a chemical bond, the stability of the molecular structure is ensured, and the use performance is improved;
(2) the preparation method of the water-soluble graphene has the advantages of short route and easy implementation, and can be used for producing water-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 water-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 water-soluble graphene, comprising the following steps:
utilizing ultrasonic wave to assist dispersion, preparing 40mL of 0.4mg/mL graphene oxide tetrahydrofuran solution, adding 0.1g of ammonium chloride under stirring, ultrasonically mixing for 10min at room temperature, heating to 68 ℃ under mechanical stirring, carrying out reflux reaction for 2h, filtering with a 0.5-micrometer filter membrane, dispersing a filter cake into 20mL of dimethyl sulfoxide under the ultrasonic action, adding 0.58g of triethyl orthoformate and 0.75g of 3-aminopropanol, heating to 140 ℃ under stirring, reacting for 5h, filtering with a 0.22-micrometer filter membrane after the reaction is finished, washing with 5mL of deionized water for 1 time, and carrying out vacuum drying at 60 ℃ for 4h to obtain the water-soluble graphene.
Structural characterization: infrared Spectrum (FT-IR) showed a hydroxyl absorption peak at 3440 and 2930cm-1And 2854cm-1Shows a characteristic peak of methylene, and the proto-graphene oxide is at 1726cm-1The carbonyl peak of (2) was shifted to 1593cm-1Here, the formation of a new bond is illustrated, with the aminopropanol successfully bound to the graphene.
Dispersing performance: the concentration value of the obtained water-soluble graphene in water is 1.27mg/mL, and the stability of the dispersion liquid is more than 6 months.
Example 2:
a preparation method of water-soluble graphene, comprising the following steps:
preparing 20mL of 0.5mg/mL oxidized graphene glycol dimethyl ether solution by ultrasonic-assisted dispersion, adding 1.0g of ammonia water under stirring, reacting for 3 hours at 80 ℃, performing vacuum filtration by using fine-pore filter paper, dispersing a filter cake into 15mLN, N-dimethylformamide, adding 0.6g of trimethyl orthoformate and 0.55g of diethanolamine, uniformly stirring, transferring into a hydrothermal reaction kettle, sealing, heating to 150 ℃ for reaction for 6 hours, cooling, taking out, filtering by using a 0.22 mu m filter membrane, washing for 1 time by using 5mL of deionized water, washing for 1 time by using 5mL of absolute ethyl alcohol, and performing vacuum drying for 2 hours at 70 ℃ to obtain the water-soluble graphene.
Structural characterization: infra red Spectroscopy (FT-IR) at 3444cm-1Shows a strong absorption of hydroxyl groups at 2923cm-1And 2849cm-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 at (a) changed, indicating that diethanolamine was successfully bound to graphene.
Dispersing performance: the concentration value of the obtained water-soluble graphene in water is 1.31mg/mL, and the stability of the dispersion liquid is more than 6 months.
Example 3:
a preparation method of water-soluble graphene, comprising the following steps:
utilizing ultrasonic wave to assist dispersion, preparing 20mL of 0.6mg/mL graphene oxide N, N-dimethylformamide solution, adding 0.6g of ammonium carbonate under stirring, reacting at 120 ℃ for 2.5h, then carrying out vacuum filtration by using a 0.22-micron filter membrane, dispersing a filter cake into 15mL of N-methyl pyrrolidone, adding 0.5g of triethyl orthoformate and 0.40g of ethylene glycol, heating to 150 ℃ under stirring for reaction for 5h, cooling, carrying out high-speed centrifugal separation, washing 3 times by using 2mL of anhydrous ethanol each time, and carrying out vacuum drying at 70 ℃ for 2h to obtain the water-soluble graphene.
Structural characterization: infra-red spectroscopy (FT-IR) at 3450cm-1Shows an absorption of hydroxyl groups at 2924cm-1And 2848cm-1Shows a characteristic peak of methylene, and the proto-graphene oxide is at 1726cm-1The carbonyl peak of (A) was transferred to 1668cm-1At 1030cm-1The nearby C-O absorption changes, indicating successful incorporation of ethylene glycol onto graphene.
Dispersing performance: the concentration value of the obtained water-soluble graphene in water is 1.15mg/mL, and the stability of the dispersion liquid is more than 6 months.
Example 4
A preparation method of water-soluble graphene, comprising the following steps:
preparing 20mL of 0.56mg/mL oxidized graphene ethylene glycol dibutyl ether solution by using ultrasonic-assisted dispersion, adding 1.0g of ammonia water under stirring, reacting at 80 ℃ for 3 hours, performing vacuum filtration by using fine-pore filter paper, dispersing a filter cake into 15mL of sulfolane, adding 0.8g of trimethyl orthoformate and 0.65g of xylitol, uniformly stirring, transferring into a hydrothermal reaction kettle, exhausting air by using nitrogen, sealing, heating to 130 ℃ for reaction for 10 hours, cooling, taking out, filtering by using a 0.22-micrometer filter membrane, washing by using 5mL of absolute ethyl alcohol for 1 time, and performing vacuum drying at 70 ℃ for 2 hours to obtain the water-soluble graphene.
Structural characterization: infra red Spectroscopy (FT-IR) at 3455cm-1Shows a strong absorption of hydroxyl groups at 2928cm-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 absorption of C-O is changed, which indicates that the xylitol is successfully combined on the graphene.
Dispersing performance: the concentration value of the obtained water-soluble graphene in water is 1.40mg/mL, and the stability of the dispersion liquid is more than 6 months.
Example 5:
a preparation method of water-soluble graphene, comprising the following steps:
preparing 20mL of 0.60mg/mL graphene oxide aqueous solution, adding 1.0g of ammonia water under stirring, performing reflux reaction for 6 hours, performing vacuum filtration by using a fine-pore filter paper, dispersing a filter cake into 15mL nitrobenzene, adding 0.8g of triethyl orthoformate and 0.60g of glycine, uniformly stirring, transferring into a hydrothermal reaction kettle, exhausting air by using nitrogen, sealing, heating to 120 ℃, reacting for 7 hours, cooling, taking out, filtering by using a 0.22-micrometer filter membrane, washing for 1 time by using 5mL of anhydrous ethanol, and performing vacuum drying for 2 hours at 70 ℃ to obtain the water-soluble graphene.
Structural characterization: infra-red spectroscopy (FT-IR) at 3452cm-1Shows a strong absorption of hydroxyl groups at 2927cm-1And 2850cm-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 changes, indicating that sorbitol was successfully bound to graphene.
Dispersing performance: the concentration value of the obtained water-soluble graphene in water is 1.05mg/mL, and the stability of the dispersion liquid is more than 6 months.
Examples 6 to 9:
a preparation method of water-soluble graphene, comprising the following steps:
preparing 100mL of 0.60mg/mL oxidized graphene glycol solution, adding 1.0g of ammonium acetate under stirring, carrying out reflux reaction for 7 hours, filtering by using a fine-pore filter paper, dividing a filter cake into 4 equal parts, respectively dispersing into 30 mLN-methyl pyrrolidone under ultrasonic waves, respectively adding 0.8g of triethyl orthoformate, respectively adding 0.60g of sorbitol, 0.54g of 2-amino-1, 3-dipropyl alcohol, 0.65g of glucose and 0.60g of glycerol, uniformly stirring, transferring into a hydrothermal reaction kettle, purging air by using nitrogen, sealing, heating to 140 ℃, reacting for 8 hours, cooling, taking out, filtering by using a filter membrane of 0.22 mu m, washing for 1 time by using 5mL of absolute ethyl alcohol, and carrying out vacuum drying at 70 ℃ for 2 hours to obtain the water-soluble graphene.
Structural characterization: infrared Spectroscopy (FT-IR) showed 4 products at 3440cm-1The left and right shows strong absorption of hydroxyl at 2920cm-1～2850cm-1Characteristic peaks for methylene are shown.
Dispersing performance: the dispersion concentration values of the obtained 4 water-soluble graphene products in water are all more than 1.0mg/mL, and the stability of the dispersion liquid is more than 6 months.
Examples 10 to 12:
a preparation method of water-soluble graphene, comprising the following steps:
preparing 100mL of 0.60mg/mL graphene oxide ethanol solution, adding 1.0g of ammonium nitrate under stirring, carrying out reflux reaction for 7h, filtering with a filter membrane, dividing a filter cake into 3 equal parts, dispersing into 40mL formamide under ultrasonic treatment, adding 0.8g of triethyl orthoformate, adding 0.65g of aminoethanesulfonic acid, 0.60g of sulfanilic acid and 0.65g of p-hydroxyphenylsulfonic acid, stirring uniformly, transferring into a hydrothermal reaction kettle, exhausting air with nitrogen, sealing, heating to 150 ℃, reacting for 8h, cooling, taking out, filtering with a 0.22 mu m filter membrane, washing with 5mL of absolute ethyl alcohol for 1 time, and carrying out vacuum drying at 70 ℃ for 2h to obtain the water-soluble graphene.
Structural characterization: infrared Spectroscopy (FT-IR) showed 3 products at 1200cm-1The strong absorption characteristic peaks of the sulfonic acid are shown on the left and right, indicating that the molecules are already present on the graphene surface.
Dispersing performance: the dispersion concentration values of the obtained aminoethanesulfonic acid, sulfanilic acid and p-hydroxyphenylsulfonic acid modified water-soluble graphene products in water are 1.38mg/mL, 1.24mg/mL and 1.21mg/mL respectively, and the stability of each dispersion is more than 6 months.
Claims (10)
1. A preparation method of water-soluble graphene is characterized by dispersing graphene oxide in a solvent A, adding an ammonia reducing agent to perform partial reduction reaction, filtering, dispersing a filter cake in a solvent B, adding a water-soluble micromolecule compound containing hydroxyl and orthoformate, reacting under a certain condition, and separating to obtain the water-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 preparation method according to claim 1, wherein the solvent A is one or a mixture of dibutyl 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, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, benzene, toluene, xylene, and nitrobenzene, and the amount of the solvent used is 50-10000 times, preferably 500-1500 times, of the mass of the graphene oxide.
4. The preparation method according to claim 1, wherein the ammonia reducing agent is ammonia water, ammonium acetate, ammonium carbonate, ammonium sulfate, ammonium nitrate or ammonium chloride, and the amount of the ammonia reducing agent added is 0.01 to 20 times, preferably 0.1 to 1.5 times, the mass of the graphene oxide.
5. The preparation method according to claim 1, wherein the reduction reaction is carried out in a normal pressure vessel or a high pressure reactor, and is carried out at a reaction temperature of 20-200 ℃ for 1-48 h.
6. The method of claim 1, wherein the dispersing step of the filter cake into the solvent B is mechanical stirring, ultrasonic dispersing, or a combination thereof.
7. The preparation method according to claim 1, wherein the solvent B is one of acetonitrile, 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, or a mixed solvent thereof, and the amount of the solvent used 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 water-soluble small molecule compound having a hydroxyl group or an amino group is ethanolamine, diethanolamine, triethanolamine, aminopropanol, aminobutanol, aminopentanol, aminohexanol, 2-amino-1, 3-propanediol, 3-amino-1, 2-propanediol, aminobutanediol, trimethylolaminomethane, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, butanetetraol, pentaerythritol, xylitol, sorbitol, mannitol, vitamin C, chitosan, fructose, glucose, dextran, maltose, hyaluronic acid; natural amino acids such as lysine, tryptophan, threonine, serine, phenylalanine, and arginine; aminoalkyl acids such as glycine, aminopropionic acid, aminobutyric acid, and aminopentanoic acid; aminoalkylsulfonic acids such as aminomethanesulfonic acid, aminoethanesulfonic acid, and aminopropanesulfonic acid; aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, hydroxybenzenesulfonic acid, hydroxyalkylsulfonic acid; dialkylamines such as ethylenediamine, propylenediamine, and butylenediamine; diethylenetriamine, triethylene tetramine, tetraethylenepentamine and pentaethylenehexamine.
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.
10. The preparation method according to claim 1, wherein the reaction is carried out in a normal pressure vessel or an autoclave under a certain condition, the reaction temperature is between room temperature and 200 ℃, the reaction time is between 0.1 and 48 hours, and the reaction time is preferably between 80 and 200 ℃ for 4 to 8 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111204750A (en) * | 2020-01-22 | 2020-05-29 | 上海应用技术大学 | Modified graphene and preparation method and application thereof |
| CN114805722A (en) * | 2022-04-22 | 2022-07-29 | 深圳环能石墨烯科技有限公司 | Graphene modified waterborne polyurethane composite material and preparation method thereof |
| WO2024002400A1 (en) * | 2022-07-01 | 2024-01-04 | Univerzita Palackeho V Olomouci | Amino-sulfonic acid-functionalized graphene for use as a catalyst |
| CN117658103A (en) * | 2023-12-07 | 2024-03-08 | 湖南科舰能源发展有限公司 | Preparation method of soft carbon negative electrode material for lithium battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445167A (en) * | 2014-11-28 | 2015-03-25 | 湖南科技大学 | Preparation method of water-soluble graphene |
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- 2018-06-22 CN CN201810648706.7A patent/CN110627052A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445167A (en) * | 2014-11-28 | 2015-03-25 | 湖南科技大学 | Preparation method of water-soluble graphene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111204750A (en) * | 2020-01-22 | 2020-05-29 | 上海应用技术大学 | Modified graphene and preparation method and application thereof |
| CN114805722A (en) * | 2022-04-22 | 2022-07-29 | 深圳环能石墨烯科技有限公司 | Graphene modified waterborne polyurethane composite material and preparation method thereof |
| WO2024002400A1 (en) * | 2022-07-01 | 2024-01-04 | Univerzita Palackeho V Olomouci | Amino-sulfonic acid-functionalized graphene for use as a catalyst |
| CN117658103A (en) * | 2023-12-07 | 2024-03-08 | 湖南科舰能源发展有限公司 | Preparation method of soft carbon negative electrode material for lithium battery |
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