CN108793134B - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN108793134B CN108793134B CN201810893388.0A CN201810893388A CN108793134B CN 108793134 B CN108793134 B CN 108793134B CN 201810893388 A CN201810893388 A CN 201810893388A CN 108793134 B CN108793134 B CN 108793134B
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/19—Preparation by exfoliation
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a preparation method of graphene, which comprises the following steps: step 1, stripping graphite by a supercritical carbon dioxide stripping method, dispersing obtained graphite powder in deionized water, crushing by a homogenizer, controlling the pressure to be 90-150 MPa, and sequentially dispersing and drying; step 2, soaking and washing the dried product obtained in the step 1 by using dilute hydrochloric acid, wherein the soaking temperature is-10-15 ℃, the soaking time is 1-4 hours, and the mass ratio of the dilute hydrochloric acid to the graphite is (1-2.5): and 1, adding a compound of potassium dichromate and hydroperoxide, carrying out oxidation reaction at the reaction temperature of 10-85 ℃ for 2.5-6 h, and after the reaction is finished, sequentially carrying out water washing, suction filtration and drying to obtain the graphene oxide powder. The aminated graphene prepared by the preparation method of graphene has small sheet diameter and low layer number, is favorable for dispersion in a matrix material when a high polymer material is modified, avoids agglomeration, and can achieve better modification effect under the condition of small addition amount.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to a preparation method of graphene.
Background
The graphene oxide prepared by the conventional oxidation-reduction method has great damage to graphene sheets, so that the performance of the graphene is reduced, and the modification application in high polymer materials is further influenced. Therefore, a method for preparing graphene with high efficiency and mass production is needed.
Disclosure of Invention
First, technical problem to be solved
The technical problem to be solved by the invention is to provide a preparation method of graphene, so as to solve the technical problem.
Second, technical scheme
In order to solve the technical problem, the technical scheme adopted by the invention is as follows: a preparation method of graphene comprises the following steps:
step 1, stripping graphite by a supercritical carbon dioxide stripping method, dispersing obtained graphite powder in deionized water, crushing by a homogenizer, controlling the pressure to be 90-150 MPa, and sequentially dispersing and drying;
step 2, soaking and washing the dried product obtained in the step 1 by using dilute hydrochloric acid, wherein the soaking temperature is-10-15 ℃, the soaking time is 1-4 hours, and the mass ratio of the dilute hydrochloric acid to the graphite is (1-2.5): 1, adding a compound of potassium dichromate and hydroperoxide, carrying out oxidation reaction at a reaction temperature of 10-85 ℃ for 2.5-6 h, and after the reaction is finished, sequentially carrying out water washing, suction filtration and drying to obtain graphene oxide powder, wherein the mass ratio of graphite to potassium dichromate to hydroperoxide is 1 (0.1-0.9) to 0.05-0.1;
and 3, dispersing the graphene oxide powder obtained in the step 2 in a solvent, adding a chlorinating agent at the temperature of-20-15 ℃, heating to 50-120 ℃ after dropwise adding for 1-4 h, reacting for 12-24 h, slowly adding a proper amount of water until no gas is generated in the system, performing suction filtration and washing, and dispersing the suction filtration product in the solvent again, wherein the mass ratio of the chlorinating agent to the graphene oxide powder is (0.3-2.8): 1;
and 4, dropwise adding ethylenediamine into the dispersion liquid obtained in the step 3, performing suction filtration and solvent washing after reacting for 10-24 hours at the temperature of 180-220 ℃ and under the pressure of 0.25-0.6 MPa, and finally dispersing the obtained filter cake in deionized water to obtain the aminated graphene aqueous slurry, wherein the mass ratio of the ethylenediamine to the chlorinating agent is (0.5-1.5): 1;
and 5, drying the aminated graphene aqueous slurry obtained in the step 4 to obtain aminated graphene powder.
The solvent in the step 3 and the step 4 is one or more selected from N, N-dimethylformamide, dichloromethane, toluene, xylene and carbon tetrachloride.
The chlorinating agent in the step 3 is one or more selected from phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride and sulfuryl chloride.
The dispersion modes in the steps 1-4 are all composite dispersion modes in which ultrasound, shearing and emulsification are carried out simultaneously.
The drying mode in the steps 1-5 is airflow type spray drying, and the temperature of the airflow type spray drying is 150-230 ℃.
Third, beneficial effect
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, firstly, graphite is physically and mechanically stripped and then oxidized, and the use amount of an oxidant and an oxidation auxiliary agent is reduced by adopting a stripping mode, so that the damage to a lamellar structure of graphene in an oxidation process is small, the oxygen content is reduced, the performance of the graphene cannot be reduced, the modification effect of the graphene can be fully exerted in an application process, and an ideal modification effect is achieved;
2. according to the preparation method of the graphene, the oxidant is added in a compound mixture of the main catalyst and the cocatalyst, compared with the traditional method of adding the oxidant step by step, the method is simple, safe and efficient, and can play a mutual synergistic effect, so that the oxidation efficiency is high, and the dosage of the oxidant is reduced;
3. according to the preparation method of the graphene, the chloridizing agent is high in reaction activity, hydroxyl and carboxyl on a graphene oxide sheet layer can be simultaneously activated, and then the graphene oxide sheet layer reacts with diamine to form a terminal amino-terminated branched chain, and simultaneously reacts with an epoxy group and diamine which cannot react with the chloridizing agent to form an amino-terminated branched chain;
4. according to the preparation method of the graphene, which is adopted by the invention, the reaction is carried out under the conditions of high temperature and high pressure, unstable groups can be lost under the conditions of high temperature and high pressure, the group reaction probability is increased on the one hand, the graphene can be further stripped under the conditions of high temperature and high pressure, and meanwhile, the stability of the modified groups is verified through the reaction under the conditions of high temperature and high pressure, so that the groups still exist when the amination graphene is subjected to the reaction modification under the conditions of high temperature and high pressure, and the chemical connection in-situ modification is realized;
5. according to the preparation method of the graphene, after the chlorinating agent participates in the reaction, water is utilized to decompose excessive chlorinating agent, and generated gas is treated by tail gas, so that the influence on environment, personnel and equipment caused by volatilization of the excessive chlorinating agent in the suction filtration and washing process and generation of a large amount of smoke due to contact with air is avoided;
6. according to the preparation method of the graphene, the graphene surface modification group is firstly reacted with the chlorinating agent and then reacted with the diamine, so that the stability of the graphene surface modification group is improved, the nitrogen content of the aminated graphene is greatly improved, the nitrogen content is improved in the modification process of the high polymer material, and the proportion of carbon and nitrogen elements is controlled to be in a reasonable range to contribute to improving the flame retardant property of the matrix material by adjusting the addition proportion of modification;
7. according to the preparation method of the graphene, the crushing and the compound dispersion mode of ultrasonic, shearing and emulsifying are simultaneously carried out by the homogenizer, the dispersion effect is better, the obtained graphene oxide has small sheet diameter and low layer number, the contact area of the modifier and the graphene oxide is greatly enhanced, and the modification effect is improved;
8. the aminated graphene prepared by the preparation method of graphene has small sheet diameter and low layer number, is favorable for dispersion in a matrix material when a high polymer material is modified, avoids agglomeration, and can achieve better modification effect under the condition of small addition amount.
Detailed Description
The following describes in detail a specific embodiment of the present invention with reference to examples.
Example 1
The invention relates to a graphene preparation method, which comprises the following steps:
step 1, stripping 100kg of graphite powder by a supercritical carbon dioxide method, adding 500kg of water into the obtained graphite powder, crushing the obtained slurry by a homogenizer with the pressure of 90MPa, processing the crushed slurry by a composite dispersion mode of ultrasound, shearing and emulsification, and drying the crushed slurry at the drying temperature of 150 ℃.
And 2, adding the dried product into 100kg of dilute hydrochloric acid at the temperature of minus 10 ℃ for soaking, adding a compound of potassium dichromate and hydroperoxide after 4 hours, controlling the mass of the potassium dichromate and the mass of the hydroperoxide to be 10kg, reacting for 2.5 hours, adding 400kg of deionized water, performing suction filtration and washing, and finally drying to obtain graphene oxide powder, wherein the drying temperature is 160 ℃.
And 3, dispersing the graphene oxide powder obtained in the step 2 in 200kg of dichloromethane in a composite dispersion mode of ultrasound, shearing and emulsification, adding thionyl chloride at the temperature of-20 ℃, wherein the mass ratio of the thionyl chloride to the graphene oxide powder is 0.3:1, heating to 50 ℃ after 1 hour after the dropwise addition is finished, condensing and refluxing in the reaction process, simultaneously absorbing tail gas, slowly adding a proper amount of water after 24 hours of reaction until no gas is generated in the system, performing suction filtration and washing, and dispersing the suction filtration product in 200kg of dichloromethane again.
And 4, dropwise adding ethylenediamine into the dispersion liquid obtained in the step 3 at normal temperature, reacting for 24 hours at 180 ℃ and 0.25MPa with the mass ratio of ethylenediamine to thionyl chloride being 0.5:1, carrying out suction filtration and washing with a solvent (dichloromethane) after the reaction is finished, and finally dispersing in deionized water in a composite dispersion mode of ultrasound, shearing and emulsification to obtain the aminated graphene aqueous slurry.
And 5, drying the aminated graphene aqueous slurry obtained in the step 4 at the drying temperature of 190 ℃ to obtain aminated graphene powder.
And (3) adding water in the step 2 in a volume which is 1-4 times that of the dilute hydrochloric acid.
The nitrogen element, the sheet diameter and the sheet thickness of the aminated graphene of the present example were measured, and the obtained results are shown in table 1; meanwhile, the aminated graphene of the embodiment is used for carrying out composite modification on PA6, and the tensile strength, the elongation at break, the maximum bending strength, the impact strength and the oxygen index of the composite material are tested, and the obtained results are shown in Table 2.
Example 2
The embodiment 2 is a graphene preparation method, which includes the following steps:
step 1, stripping 100kg of worm graphite by supercritical carbon dioxide, adding 500kg of water into the obtained graphite powder, crushing the obtained slurry by a homogenizer at the pressure of 150MPa, processing the crushed slurry in a composite dispersion mode of ultrasound, shearing and emulsification, drying the crushed slurry by airflow spray drying at the drying temperature of 230 ℃,
and 2, adding the dried product into 250kg of dilute hydrochloric acid for soaking at 15 ℃, adding a compound mixture of potassium dichromate and hydroperoxide after 1h, controlling the temperature to be 85 ℃, adding 400kg of deionized water after 6h of reaction, performing suction filtration and washing, and finally performing air-flow spray drying to obtain graphene oxide powder, wherein the drying temperature is 230 ℃.
And 3, dispersing the graphene oxide powder obtained in the step 2 in 200kg of toluene in a composite dispersion mode of ultrasound, shearing and emulsification, dropwise adding phosphorus trichloride at the temperature of-20 ℃, wherein the mass ratio of the phosphorus trichloride to the graphene oxide powder is 2.8:1, heating to 120 ℃ after 1 hour after the dropwise addition is finished, condensing and refluxing in the reaction process, simultaneously absorbing tail gas, slowly adding a proper amount of water after reacting for 12 hours until no gas is generated in the system, performing suction filtration and washing, and re-dispersing the suction filtration product in 200kg of toluene.
And 4, dropwise adding ethylenediamine into the dispersion liquid obtained in the step 3 at normal temperature, reacting for 10 hours at 220 ℃ and 0.6MPa, wherein the mass ratio of ethylenediamine to phosphorus trichloride is 1.5:1, performing suction filtration and solvent (toluene) washing after the reaction is finished, and finally dispersing in deionized water in a composite dispersion mode of ultrasound, shearing and emulsification to obtain the aminated graphene aqueous slurry.
And 5, drying the aminated graphene aqueous slurry obtained in the step 4 by airflow spray drying at the drying temperature of 190 ℃ to obtain aminated graphene powder.
The nitrogen element, the sheet diameter and the sheet thickness of the aminated graphene of the embodiment are tested, and the obtained results are shown in table 1; meanwhile, the aminated graphene of the embodiment is used for carrying out composite modification on PA6, and the tensile strength, the elongation at break, the maximum bending strength, the impact strength and the oxygen index of the composite material are tested, and the obtained results are shown in Table 2.
Example 3
The embodiment 3 is a graphene preparation method, which includes the following steps:
step 1, peeling 100kg of crystalline flake graphite by supercritical carbon dioxide, adding 500kg of water into the obtained graphite powder, crushing the obtained slurry by a homogenizer with the pressure of 110MPa, processing the crushed slurry by a composite dispersion mode of ultrasound, shearing and emulsification, drying the crushed slurry by airflow spray drying at the drying temperature of 170 ℃,
and 2, adding the dried product into 120kg of dilute hydrochloric acid for soaking at-1 ℃, adding a compound mixture of potassium dichromate and hydroperoxide after 2 hours, controlling the mass of the potassium dichromate and the mass of the hydroperoxide to be 9kg, controlling the temperature to be 55 ℃, adding 300kg of deionized water after 3.5 hours of reaction, performing suction filtration and washing, and finally performing air-flow spray drying to obtain graphene oxide powder, wherein the drying temperature is 170 ℃.
And 3, dispersing the graphene oxide powder obtained in the step 2 in 250kg of dimethylbenzene in a composite dispersion mode of ultrasound, shearing and emulsification, dropwise adding phosphorus pentachloride at 15 ℃, wherein the mass ratio of the phosphorus pentachloride to the graphene oxide powder is 0.5:1, heating to 90 ℃ after the dropwise addition is completed for 2 hours, condensing and refluxing in the reaction process, simultaneously absorbing tail gas, slowly adding a proper amount of water after reacting for 16 hours until no gas is generated in the system, performing suction filtration and washing, and re-dispersing the suction filtration product in 200kg of dimethylbenzene.
And 4, dropwise adding ethylenediamine into the dispersion liquid obtained in the step 3 at normal temperature, reacting for 13 hours at 200 ℃ and 0.55MPa, wherein the mass ratio of ethylenediamine to phosphorus pentachloride is 0.7:1, performing suction filtration and washing after the reaction is finished, and finally dispersing in deionized water in a composite dispersion mode of ultrasound, shearing and emulsification to obtain the aminated graphene aqueous slurry.
And 5, drying the aminated graphene aqueous slurry obtained in the step 4 by airflow spray drying at the drying temperature of 180 ℃ to obtain aminated graphene powder.
The nitrogen element, the sheet diameter and the sheet thickness of the aminated graphene of the embodiment are tested, and the obtained results are shown in table 1; meanwhile, the aminated graphene of the embodiment is used for carrying out composite modification on PA6, and the tensile strength, the elongation at break, the maximum bending strength, the impact strength and the oxygen index of the composite material are tested, and the obtained results are shown in Table 2.
Comparative example 1
The comparative example is basically the same as example 1, except that graphite is directly soaked in dilute hydrochloric acid without physical stripping and crushing and dispersing, the nitrogen element, the sheet diameter and the sheet thickness of the aminated graphene of the comparative example are tested, the obtained results are shown in table 1, the aminated graphene of the comparative example is used for carrying out composite modification on PA6, and the tensile strength, the elongation at break, the maximum bending strength, the impact strength and the oxygen index of the composite material are tested, and the obtained results are shown in table 2.
Comparative example 2
The comparative example is basically the same as example 1, except that the obtained graphene oxide slurry directly reacts with ethylenediamine, nitrogen element, sheet diameter and sheet thickness of the aminated graphene of the comparative example are tested, and meanwhile, the aminated graphene of the comparative example is used for carrying out composite modification on PA6, so that tensile strength, elongation at break, maximum bending strength, impact strength and oxygen index of the composite material are tested, and the obtained results are respectively shown in tables 1 and 2.
Comparative example 3
The comparative example is basically the same as example 1, except that the amounts of concentrated sulfuric acid, potassium permanganate and hydrogen peroxide are designed according to a conventional preparation method of graphene oxide, nitrogen elements, sheet diameters and sheet thicknesses of the aminated graphene of the comparative example are tested, meanwhile, the aminated graphene of the comparative example is used for carrying out composite modification on PA6, and the tensile strength, the elongation at break, the maximum bending strength, the impact strength and the oxygen index of the composite material are tested, and the obtained results are respectively shown in tables 1 and 2.
Comparative example 4
This comparative example is a pure PA6 sample for comparison with PA6 modified with addition of aminated graphene, and as comparative example 4 the tensile strength, elongation at break, maximum flexural strength, impact strength and oxygen index of the material were tested and the results are shown in table 2.
Table 1 test results of aminated graphene prepared in each example and comparative example
| GO sheet diameter (nm) | GO (nm) | N content (%) | |
| Example 1 | 200 | 1.3 | 18.5 |
| Example 2 | 350 | 1.6 | 19.2 |
| Example 3 | 270 | 1.4 | 18.9 |
| Comparative example 1 | 3500 | 4.0 | 13.2 |
| Comparative example 2 | 620 | 1.7 | 8.0 |
| Comparative example 3 | 380 | 1.5 | 22.1 |
As can be seen from table 1, the aminated graphene prepared by the method of the present invention has a smaller sheet diameter, a smaller sheet thickness, and a higher nitrogen content than aminated graphene prepared by a method without physical exfoliation and crushing dispersion and a method directly using ethylenediamine for modification, because aminated graphene prepared without physical exfoliation and crushing dispersion has a larger sheet diameter, a thicker sheet layer, fewer surface groups, and a lower nitrogen content because the modified small molecules cannot sufficiently contact with the graphene sheet layer during modification, and the modification effect is poor. The thickness and the sheet diameter of the sheet layer of the aminated graphene prepared by the conventional oxidation method are not much different from those of the aminated graphene prepared by the method, and the nitrogen content is higher, because the conventional oxidation method has higher oxidation degree and more surface oxygen-containing groups, but the high oxidation degree brings the consequence of higher sheet layer destruction to the graphene and influences the modification effect. The modification method of the invention has good modification effect, and the surface oxygen-containing groups are all converted into amino-terminated branched chains, so the nitrogen content is increased.
TABLE 2 test results of the composites obtained in the examples and comparative examples
As can be seen from table 2, the PA6 modified by the graphene prepared by the method of the present invention has significantly improved tensile strength, maximum bending strength, and impact strength, because the aminated graphene is connected to the substrate in the form of chemical bonds in the substrate, and the interface acting force is large. The flame retardance of the material is also obviously improved because the graphene prepared by the method has higher nitrogen content, smaller damage degree of graphene sheet layers and better coordinated flame retardant effect. As can be seen from comparative example 3, the graphene oxide prepared by the conventional oxidation method has great damage to the sheet layer, and the increase of the oxygen content brings influence on the flame retardant effect. Meanwhile, the aminated graphene modified PA6 prepared by the method has low elongation at break, and the characteristic of the aminated graphene modified PA6 meets the requirement that the elongation at break is 15-20% of the conventional PA6 industrial yarn, which cannot be achieved by the conventional PA6 product.
The above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way.
Claims (1)
1. A preparation method of graphene is characterized by comprising the following steps:
step 1, stripping graphite by a supercritical carbon dioxide stripping method, dispersing obtained graphite powder in deionized water, crushing by a homogenizer, controlling the pressure to be 90-150 MPa, and sequentially dispersing and drying;
step 2, soaking and washing the dried product obtained in the step 1 by using dilute hydrochloric acid, wherein the soaking temperature is-10-15 ℃, the soaking time is 1-4 hours, and the mass ratio of the dilute hydrochloric acid to the graphite is (1-2.5): 1, adding a compound of potassium dichromate and hydroperoxide, carrying out oxidation reaction at a reaction temperature of 10-85 ℃ for 2.5-6 h, and after the reaction is finished, sequentially carrying out water washing, suction filtration and drying to obtain graphene oxide powder, wherein the mass ratio of graphite to potassium dichromate to hydroperoxide is 1 (0.1-0.9) to 0.05-0.1;
and 3, dispersing the graphene oxide powder obtained in the step 2 in a solvent, adding a chlorinating agent at the temperature of-20-15 ℃, heating to 50-120 ℃ after dropwise adding for 1-4 h, reacting for 12-24 h, slowly adding a proper amount of water until no gas is generated in the system, performing suction filtration and washing, and dispersing the suction filtration product in the solvent again, wherein the mass ratio of the chlorinating agent to the graphene oxide powder is (0.3-2.8): 1;
and 4, dropwise adding ethylenediamine into the dispersion liquid obtained in the step 3, performing suction filtration and solvent washing after reacting for 10-24 hours at the temperature of 180-220 ℃ and under the pressure of 0.25-0.6 MPa, and finally dispersing the obtained filter cake in deionized water to obtain the aminated graphene aqueous slurry, wherein the mass ratio of the ethylenediamine to the chlorinating agent is (0.5-1.5): 1;
step 5, drying the aminated graphene aqueous slurry obtained in the step 4 to obtain aminated graphene powder;
the solvent in the step 3 and the step 4 is selected from one or more of N, N-dimethylformamide, dichloromethane, toluene, xylene and carbon tetrachloride;
the chlorinating agent in the step 3 is one or more selected from phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride and sulfuryl chloride;
the dispersion modes in the steps 1-4 are all composite dispersion modes in which ultrasound, shearing and emulsification are carried out simultaneously;
the drying mode in the steps 1-5 is airflow type spray drying, and the temperature of the airflow type spray drying is 150-230 ℃.
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| CN112408374A (en) * | 2020-11-27 | 2021-02-26 | 浙江工业大学 | Method for reducing graphene agglomeration |
| CN115261002B (en) * | 2021-04-30 | 2024-03-01 | 中国石油天然气股份有限公司 | Superparamagnetism graphene oxide oil displacement agent and preparation method thereof |
| CN116854549A (en) * | 2023-07-26 | 2023-10-10 | 中国工程物理研究院化工材料研究所 | Method for cooperatively improving mechanical and heat conducting properties of mixed explosive and obtained mixed explosive |
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Effective date of registration: 20220124 Address after: 528400 west side of floor 3, building e, Du Zehui and Liang Guixin plant, Qiye South Road, Maxin Industrial Zone, Huangpu town, Zhongshan City, Guangdong Province Applicant after: Zhongshan Yuetai Auto Parts Co.,Ltd. Address before: 230011 523 Mingguang Road Street, Yaohai District, Hefei City, Anhui Province Applicant before: Gao Weijia |
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