CN108751180B - Method for preparing carboxylation modified graphene by utilizing solid-phase reaction - Google Patents
Method for preparing carboxylation modified graphene by utilizing solid-phase reaction Download PDFInfo
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- CN108751180B CN108751180B CN201811041861.9A CN201811041861A CN108751180B CN 108751180 B CN108751180 B CN 108751180B CN 201811041861 A CN201811041861 A CN 201811041861A CN 108751180 B CN108751180 B CN 108751180B
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Abstract
The invention discloses a method for preparing carboxylation modified graphene by utilizing a solid-phase reaction. The method belongs to the technical field of graphene and surface treatment. The method is realized by reacting 10 parts by mass of iminodiacetic acid, 11-12 parts by mass of paraformaldehyde and 5-10 parts by mass of graphene at 180-220 ℃ under the solvent-free condition. Different from other modifications carried out in a solvent system, the key synthesis step of the preparation method disclosed by the invention adopts a solvent-free dipolar cycloaddition reaction, and breaks through the production scale limitation of a solvent-assisted modification method with a generally low reaction system concentration and the limitation of a reaction temperature selection range influenced by the boiling point of a solvent, so that the production efficiency is improved, and the production scale is favorably enlarged.
Description
Technical Field
The invention discloses a method for preparing carboxylation modified graphene by utilizing a solid-phase reaction. The method belongs to the technical field of graphene and surface treatment.
Background
Graphene has a unique single-layer structure, has excellent mechanical, electrical and thermal properties, and draws extensive attention and research hot tide in the fields of materials, energy, catalysis, biomedicine and the like. In practical application, however, due to the ultra-large specific surface area and the high surface energy of graphene, the agglomeration phenomenon is obvious, and is not favorable for the dispersion of graphene in the composite material or the solvent. In addition, in biomedical, energy and other applications, the surface functional groups of the material will play a crucial role. Therefore, the graphene surface modification research aiming at introducing functional groups on the surface of graphene so as to controllably adjust the properties of the graphene, such as structure, surface, chemistry, electricity and the like, becomes an important field of graphene application research.
In recent years, research on the functional modification of graphene has achieved a great deal of research results. The patent CN102433032, namely the synthesis method for controllably synthesizing carboxylated graphene and the obtained nano material, provides a modification method adopting an azo initiator, but the method has the defects of complex process and certain potential safety hazard. Patent No. CN104445163, "a preparation method of carboxylated graphene", discloses a feasible method for preparing carboxyl modified graphene from graphene oxide, which can obtain carboxylated graphene with good dispersibility, but the reaction process uses 1g/L to 3g/L of graphene oxide suspension, and the system concentration is limited, and the reaction time is long, which is not conducive to high-efficiency mass production.
Disclosure of Invention
The invention aims to provide a graphene modification method adopting a solid-phase reaction aiming at the defects in the prior art. The method is realized by reacting 10 parts by mass of iminodiacetic acid, 11-12 parts by mass of paraformaldehyde and 5-10 parts by mass of graphene at 180-220 ℃ under the solvent-free condition. At present, the functionalization reaction of graphene is mostly carried out in a solvent, and the commonly involved solvents include water, dimethyl sulfoxide, N, N' -dimethylformamide and the like. Due to the limited dispersibility of graphene in these solvents, reaction concentrations of many grams per liter are generally employed. Furthermore, when the reaction is carried out under normal pressure, the boiling point of these solvents is more than 200 ℃. Unlike these modifications in solvent systems, the key synthetic steps of the preparation method disclosed by the invention adopt a solvent-free dipolar cycloaddition reaction, and break through the limitations of production scale limited by low reaction system concentration and reaction temperature selection range influenced by the boiling point of the solvent. The input of solid powdery material is much greater than the reactant content of the low-concentration dispersion in the same reactor volume. Thereby improving the yield obtained by the reaction scale with the same volume in unit time and being beneficial to enlarging the production scale. In addition, in order to realize the preparation reaction at higher temperature, organic solvents such as dimethyl sulfoxide, N, N' -dimethylformamide and the like are mostly adopted in the solvent-assisted modification reaction, the removal of the solvents is relatively difficult, and the solvents have toxicity.
The purpose of the invention is realized by the following technical scheme:
and (4) preparing synthesis. A stirring device is arranged at the middle opening of a three-opening reaction bottle, 10 parts by mass of iminodiacetic acid and 11-12 parts by mass of paraformaldehyde are added into the reaction bottle, 120-600 parts by mass of absolute ethyl alcohol is added, stirring and dispersing are carried out for 10-20 min, then 5-10 parts by mass of graphene is added into the reaction bottle, and stirring is carried out for 30min at room temperature. And (3) raising the temperature of the reaction bottle to 60-80 ℃, and continuously stirring at the temperature until the ethanol is completely volatilized. The heating was stopped and the flask and solid mixture were allowed to cool to room temperature. A powdery solid was obtained.
Solvent-free dipolar cycloaddition modification of graphene. And (3) installing a stirring device at the middle opening of the three-opening reaction bottle, respectively installing a reflux condenser tube and a thermocouple at the side openings of two sides, heating the reaction system to 180-220 ℃, reacting for 4-6 h, stopping heating, and naturally cooling the reaction system to room temperature to obtain a mixed product containing the carboxylated modified graphene.
And (3) separating and purifying the carboxylated modified graphene. And ultrasonically cleaning the obtained product in 200 parts by mass of a mixed solvent of water, acetone and ethanol in a mass ratio of 2:2:1 for 30min in a glass container, then performing vacuum filtration and sequentially cleaning with water, acetone and ethanol. And collecting the obtained solid, and drying in a vacuum oven at 40 ℃ for 24h to obtain the carboxylated graphene powder.
Compared with the prior art, the invention has the following advantages:
the solid-phase carboxylation modification of graphene is realized;
the method is simple and easy to operate, and the number of intermediate steps is small;
the solid-phase reaction is not limited by the dispersibility of the graphene in a solvent, and the production scale is convenient to expand.
Detailed description of the invention
The technical solution of the present invention will be further described with reference to the following examples:
example 1:
a stirring device is arranged at the middle opening of a three-opening reaction bottle, 4g of iminodiacetic acid and 4.5g of paraformaldehyde are added into the reaction bottle, 230g of absolute ethyl alcohol is added, stirring and dispersing are carried out for 15min, then 4g of graphene is added into the reaction bottle, and stirring is carried out at room temperature for 30 min. The flask was heated to 60 ℃ and stirring continued at this temperature until complete evaporation of the solvent. The heating was stopped and the flask and solid mixture were allowed to cool to room temperature. A black powdery solid was obtained.
And (3) installing a stirring device at the middle opening of the three-opening reaction bottle, respectively installing a reflux condenser tube and a thermocouple at the side openings of two sides, heating the reaction system to 180 ℃, reacting for 6 hours, stopping heating, and naturally cooling the reaction system to room temperature to obtain a mixture containing the carboxylated modified graphene product.
Ultrasonically cleaning the obtained product in a mixed solvent of water, acetone and ethanol with the total mass of 80g and the volume ratio of 2:2:1 for 30min in a glass container, then carrying out vacuum filtration and cleaning with water, acetone and ethanol in sequence. And collecting the obtained solid, and drying in a vacuum oven at 40 ℃ for 24h to obtain the carboxylated graphene powder.
Example 2:
a stirring device is arranged at the middle opening of a three-opening reaction bottle, 40g of iminodiacetic acid and 45g of paraformaldehyde are added into the reaction bottle, 2300g of absolute ethyl alcohol is added, stirring and dispersing are carried out for 15min, then 40g of graphene is added into the reaction bottle, and stirring is carried out at room temperature for 30 min. The flask was heated to 60 ℃ and stirring continued at this temperature until complete evaporation of the solvent. The heating was stopped and the flask and solid mixture were allowed to cool to room temperature. A black powdery solid was obtained.
And (3) installing a stirring device at the middle opening of the three-opening reaction bottle, respectively installing a reflux condenser tube and a thermocouple at the side openings of two sides, heating the reaction system to 180 ℃, reacting for 6 hours, stopping heating, and naturally cooling the reaction system to room temperature to obtain a mixture containing the carboxylated modified graphene product.
Ultrasonically cleaning the obtained product in a glass container by using a mixed solvent of water, acetone and ethanol with the total mass of 800g and the volume ratio of 2:2:1 for 30min, then carrying out vacuum filtration and cleaning by using water, acetone and ethanol in sequence. And collecting the obtained solid, and drying in a vacuum oven at 40 ℃ for 24h to obtain the carboxylated graphene powder.
The difference between example 2 and example 1 is that the dosage of example two is ten times that of example one, but the product obtained in example 2 is consistent with that obtained in example 1.
Example 3:
a stirring device is arranged at the middle opening of a three-opening reaction bottle, 6g of iminodiacetic acid and 7.2g of paraformaldehyde are added into the reaction bottle, 300g of absolute ethyl alcohol is added, stirring and dispersing are carried out for 20min, then 4g of graphene is added into the reaction bottle, and stirring is carried out at room temperature for 30 min. The flask was heated to 70 ℃ and stirring continued at this temperature until complete evaporation of the solvent. The heating was stopped and the flask and solid mixture were allowed to cool to room temperature. A black powdery solid was obtained.
And (3) installing a stirring device at the middle opening of the three-opening reaction bottle, respectively installing a reflux condenser tube and a thermocouple at the side openings of two sides, heating the reaction system to 200 ℃, reacting for 5 hours, stopping heating, and naturally cooling the reaction system to room temperature to obtain a mixture containing the carboxylated modified graphene product.
Ultrasonically cleaning the obtained product in a glass container by using a mixed solvent of water, acetone and ethanol with the total mass of 120g and the volume ratio of 2:2:1 for 30min, then carrying out vacuum filtration and cleaning by using water, acetone and ethanol in sequence. And collecting the obtained solid, and drying in a vacuum oven at 40 ℃ for 24h to obtain the carboxylated graphene powder.
Example 4:
a stirring device is arranged at the middle opening of a three-opening reaction bottle, 60g of iminodiacetic acid and 72g of paraformaldehyde are added into the reaction bottle, 3000g of absolute ethyl alcohol is added, stirring and dispersing are carried out for 20min, then 40g of graphene is added into the reaction bottle, and stirring is carried out at room temperature for 30 min. The flask was heated to 70 ℃ and stirring continued at this temperature until complete evaporation of the solvent. The heating was stopped and the flask and solid mixture were allowed to cool to room temperature. A black powdery solid was obtained.
And (3) installing a stirring device at the middle opening of the three-opening reaction bottle, respectively installing a reflux condenser tube and a thermocouple at the side openings of two sides, heating the reaction system to 200 ℃, reacting for 5 hours, stopping heating, and naturally cooling the reaction system to room temperature to obtain a mixture containing the carboxylated modified graphene product.
Ultrasonically cleaning the obtained product in a glass container by using a mixed solvent of water, acetone and ethanol with the total mass of 1200g and the volume ratio of 2:2:1 for 30min, then carrying out vacuum filtration and cleaning by using water, acetone and ethanol in sequence. And collecting the obtained solid, and drying in a vacuum oven at 40 ℃ for 24h to obtain the carboxylated graphene powder.
Example 4 differs from example 3 in that the feed rate of example 4 is ten times that of example 3, but the product properties of example 4 are consistent with those of example 3.
Claims (1)
1. A method for preparing carboxylation modified graphene by utilizing solid-phase reaction is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing for synthesis, installing a stirring device at a middle opening of a three-opening reaction bottle, adding 10 parts by mass of iminodiacetic acid and 11-12 parts by mass of paraformaldehyde into the reaction bottle, adding 120-600 parts by mass of absolute ethyl alcohol, stirring and dispersing for 10-20 min, then adding 5-10 parts by mass of graphene into the reaction bottle, stirring for 30min at room temperature, raising the temperature of the reaction bottle to 60-80 ℃, continuously stirring at the temperature until the ethyl alcohol is completely volatilized, stopping heating, and naturally cooling a flask and a solid mixture to the room temperature to obtain a powdery solid;
(2) carrying out solvent-free dipolar cycloaddition modification on graphene, installing a stirring device at the middle opening of a three-opening reaction bottle, respectively installing a reflux condenser tube and a thermocouple at the side openings of two sides, heating the reaction system to 180-220 ℃, reacting for 4-6 h, stopping heating, and naturally cooling the reaction system to room temperature to obtain a mixed product containing the carboxylated modified graphene;
(3) separating and purifying the carboxylated modified graphene, ultrasonically cleaning the obtained product in a glass container for 30min by using 200 parts by mass of a mixed solvent of water, acetone and ethanol with the mass ratio of 2:2:1, then performing vacuum filtration, sequentially cleaning the product by using water, acetone and ethanol, collecting the obtained solid, and drying the solid in a vacuum oven at 40 ℃ for 24h to obtain the carboxylated graphene powder.
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| CN102433032B (en) * | 2011-09-08 | 2013-10-30 | 南京师范大学 | Controllable method for synthesizing carboxylic graphene oxide and prepared nano material |
| CN104445155B (en) * | 2013-09-17 | 2016-03-23 | 中国科学院大连化学物理研究所 | Grapheme material of a kind of carboxyl-functional and preparation method thereof |
| CN104445163B (en) * | 2014-11-14 | 2016-08-24 | 中国航空工业集团公司北京航空材料研究院 | A kind of preparation method of carboxylated Graphene |
| CN107651669B (en) * | 2017-09-22 | 2018-11-23 | 北京化工大学 | A method of reaction mill method prepares edge carboxylated graphene and graphene |
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