CN117303357A - Imidazole ionic liquid functionalized graphene and preparation method thereof - Google Patents
Imidazole ionic liquid functionalized graphene and preparation method thereof Download PDFInfo
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- CN117303357A CN117303357A CN202311310577.8A CN202311310577A CN117303357A CN 117303357 A CN117303357 A CN 117303357A CN 202311310577 A CN202311310577 A CN 202311310577A CN 117303357 A CN117303357 A CN 117303357A
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- ionic liquid
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WXJHMNWFWIJJMN-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCN1C[NH+](C)C=C1 WXJHMNWFWIJJMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- -1 1-octyl-3-methylimidazole chloride modified graphene Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
Abstract
An imidazole ionic liquid functionalized graphene and a preparation method thereof belong to the technical field of new graphene materials. Firstly, adding a solvent into imidazole ionic liquid, and adding graphene into the mixed liquid for ball milling to obtain a product; and then adding the obtained product into an organic solvent, centrifugally washing and drying, performing ultrasonic dispersion, and then freeze-drying to obtain the black powdery imidazole ionic liquid functionalized graphene. The main raw material of the preparation method is graphene, the cost is low, and the ball milling process is used, so that mass industrialized production can be performed. The imidazole ionic liquid functionalized graphene prepared by the method has good reinforcing and toughening effects, so that the imidazole ionic liquid functionalized graphene has potential application value in the fields of resin reinforcement, toughening and heat conduction.
Description
Technical Field
The invention belongs to the technical field of new graphene materials, and particularly relates to imidazole ionic liquid functionalized graphene and a preparation method thereof.
Background
The graphene is a single-layer graphite sheet with a honeycomb structure formed by sp2 hybridization, the first paper on the graphene is published in 2004, a two-dimensional material which exists stably at room temperature is prepared for the first time, the statement that the two-dimensional material cannot exist stably at room temperature is broken, and a inventor of the two-dimensional material obtains a Nobel physical prize in 2010. Because graphene has excellent mechanical and electrical properties and higher light transmittance, the graphene is paid attention to as a new member of a carbon family, and a large part of researchers are researching and preparing large-area single-layer or few-layer graphene; there are many researchers in researching and preparing graphene powder materials, wherein the redox method is the most common method for preparing graphene powder at present, and is also the most potential method for realizing large-scale preparation of graphene powder. Meanwhile, many researchers are researching graphene derivatives and hybridized materials of graphene, and after modification treatment is carried out on graphene, the modified graphene can be more suitable for requirements of related fields.
Ionic Liquids (ILs) generally are in a liquid state at room temperature, and contain an organic cation and an inorganic or organic anion in the structure. Ionic liquids, which are a new type of "green" solvents, have many unique properties compared to traditional solvent properties. After seventies of the last century, ionic liquids have attracted attention from the expert wilks who tried to make a better battery for missiles and space detectors, but from which a liquid electrolyte was found. Ionic liquids are now successfully used in a number of fields of solvent extraction, electrochemistry, separation and purification of materials, catalysts and solvents.
Patent CN110963487a reports a preparation method of ionic liquid modified graphene with wave-absorbing property, which has excellent wave-absorbing property and dispersibility, but the raw material used is graphene, which is expensive and not easy to obtain, and the preparation method comprises a grinding step, so that mass production cannot be realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides imidazole ionic liquid functionalized graphene and a preparation method thereof. The main raw material of the preparation method is graphene, the cost is low, and the ball milling process is used, so that mass industrialized production can be performed. The imidazole ionic liquid functionalized graphene prepared by the method has good reinforcing and toughening effects, so that the imidazole ionic liquid functionalized graphene has potential application value in the fields of resin reinforcement, toughening and heat conduction.
The invention aims at realizing the following technical scheme:
the preparation method of the imidazole ionic liquid functionalized graphene comprises the following steps:
step (1): adding a solvent into the imidazole ionic liquid to obtain a mixed solution; adding graphene into a ball milling tank containing grinding balls, and then adding the mixed solution into the ball milling tank for ball milling to obtain a product;
step (2): and (3) adding the product obtained in the step (1) into an organic solvent, centrifuging, washing, drying, performing ultrasonic dispersion on the dried product, and finally drying to obtain the black powdery imidazole ionic liquid functionalized graphene.
The preparation method of the imidazole ionic liquid functionalized graphene comprises the following steps:
the imidazole ionic liquid in the step (1) is one of 1-methyl-3-butyl imidazole chloride, 1-butyl-3-methyl imidazole chloride and 1-octyl-3-methyl imidazole chloride;
the solvent in the step (1) is a mixture of water and one of methanol, ethanol, THF and DMF, and the mass concentration of the organic solvent in the mixture is 50%;
the dosage ratio of the imidazole ionic liquid to the solvent in the step (1) is as follows: (1-10) g:50mL;
the graphene is reduced graphene oxide; the mass ratio of the graphene to the imidazole ionic liquid is 1 (1-10);
the ball milling tank and the grinding balls are made of zirconia; the ball-material ratio of the grinding balls to the graphene and the mixed solution in the ball milling tank is (4-6): 1; the ball milling time is 3-6h, and the ball milling revolution is 100-200rpm;
the organic solvent in the step (2) is one of methanol, ethanol, THF and DMF; the centrifugation is carried out, the centrifugal revolution is at least 10000rpm, and when the products are all accumulated at the bottom of the centrifuge tube, the upper layer of the centrifuge tube is clear liquid, the centrifugation is stopped;
the washing and drying in the step (2) are specifically carried out by firstly washing for 2-3 times by using an organic solvent and water alternately, and then drying for 10-12h in a baking oven at 60-80 ℃;
the ultrasonic dispersion in the step (2) is specifically carried out in water, the dispersion time is 5-10h, and the ultrasonic temperature is not more than 30 ℃; the drying mode after ultrasonic dispersion adopts freeze drying.
The ionic liquid functionalized graphene prepared by the ionic liquid functionalized graphene preparation method has the following structure:
wherein R is 1 And R is 2 Each independently selected from methyl, butyl, octyl;
the ionic liquid functionalized graphene is characterized in that imidazole groups in the imidazole ionic liquid and a six-membered ring structure of the graphene both belong to conjugated structures, pi-pi stacking interaction is generated between the imidazole groups and the six-membered ring structure of the graphene, and the ionic liquid is adsorbed on the surface of the graphene in a non-covalent bond mode.
The beneficial effects of the invention are as follows:
1. the preparation method of the imidazole ionic liquid functionalized graphene is simple, has low equipment requirement, is easy to obtain raw materials, and can be used for material modification.
2. The preparation method provided by the invention is simple, the conditions are easy to control, and the post-treatment is convenient.
3. The imidazole ionic liquid functionalized graphene prepared by the method has better subsequent utilization value, and can be used for obtaining a polymer containing graphene.
4. The imidazole ionic liquid functionalized graphene prepared by the invention is black solid powder, has good reinforcing and toughening effects, and is simple in preparation method, easy to control in conditions and convenient to post-treat. The invention aims to synthesize imidazole ionic liquid functionalized graphene, so that the imidazole ionic liquid functionalized graphene can have potential application value in the fields of resin reinforcement, toughening or other fields.
Drawings
FIGS. 1 a-1 b are scanning electron microscope images of graphene and ionic liquid functionalized graphene in example 1 of the present invention, respectively;
FIG. 2 is a scanning electron microscope image of the ionic liquid functionalized graphene in embodiment 3 of the present invention;
as can be seen from fig. 1 and 2, the extension of the ball milling time makes the functionalized graphene smaller in size and thinner in sheet. The method is mainly because graphene sheets can collide with balls to be crushed in the ball milling process, and the modified graphene can be crushed and peeled by prolonging the ball milling time.
Detailed Description
The invention will be described in detail with reference to examples
Example 1
The preparation method of the imidazole ionic liquid functionalized graphene comprises the following specific operation steps:
step (1): 10g of graphene and 10g of 1-methyl 3-butylimidazole chloride salt are added into a ball-milling tank after being dispersed in 50ml of 50% ethanol water solution, 300g of grinding balls are added into the ball-milling tank, and after the addition is completed, the ball-milling tank is arranged on a planetary ball mill, and ball milling is carried out for 3 hours at 150 rpm.
Step (2): dispersing the ball-milled product into ethanol, centrifuging, alternately washing twice with ethanol and distilled water, drying the product in an oven at 80 ℃, dispersing the dried product into 100ml of water, performing ultrasonic treatment for 6 hours, and then performing freeze drying to obtain black powder which is the imidazole ionic liquid functionalized graphene.
Step (3): 1.8g of ionic liquid modified graphene and 180g of ABS resin are melted and mixed at 160 ℃ and are extruded to form the ionic liquid modified graphene/ABS heat conduction composite material. Fig. 1 a-1 b are scanning electron microscope images of graphene and ionic liquid functionalized graphene in example 1, respectively.
Example 2
Step (1): as in example 1.
Step (2): dispersing the ball-milled product into methanol, centrifuging, alternately washing twice with methanol and distilled water, drying the product in an oven at 80 ℃, dispersing the dried product into 100ml of water, performing ultrasonic treatment for 10 hours, and then performing freeze drying to obtain black powder which is the imidazole ionic liquid functionalized graphene.
Example 3
Step (1): 10g of graphene and 1g of 1-octyl-3-methylimidazole chloride are added into a ball milling tank, dispersed in 50ml of 50% methanol aqueous solution, 300g of grinding balls are added into the ball milling tank, and after the addition is completed, the ball milling tank is arranged on a planetary ball mill, and ball milling is performed for 6 hours at 150 rpm.
Step (2): as in example 1.
Step (3): same as in example 1
Fig. 2 is a scanning electron microscope image of the ionic liquid functionalized graphene in example 3.
Example 4
Step (1): as in example 1.
Step (2): dispersing the ball-milled product into ethanol, performing suction filtration, alternately washing twice with ethanol and distilled water, drying the product in an oven at 80 ℃, dispersing the dried product into 100ml of water for 8 hours by ultrasonic treatment, and then performing freeze drying to obtain black powder which is the imidazole ionic liquid functionalized graphene.
Example 5
Step (1): as in example 1.
Step (2): dispersing the ball-milled product into methanol, performing suction filtration, alternately washing twice with methanol and distilled water, drying the product in an oven at 80 ℃, dispersing the dried product into 100ml of water for 8 hours by ultrasonic treatment, and then performing freeze drying to obtain black powder which is the imidazole ionic liquid functionalized graphene.
Comparative example 1
And (3) melting and mixing 1.8g of graphene with 180g of ABS resin at 160 ℃, and performing extrusion molding to obtain the graphene/ABS heat-conducting composite material.
The samples of examples 1, 3 and comparative example 1 were tested for performance, wherein the tensile strength was tested according to GB 1040-79, the flexural modulus was tested according to GB/T9341-2008, the impact strength was tested according to GB/T1843-2008, the thermal conductivity was tested according to GB/T32064-2015, and the test results are shown in Table 1:
table 1 performance testing of ionic liquid functionalized graphene/ABS thermally conductive composites
| Tensile Strength (MPa) | Flexural modulus (MPa) | Impact Strength (kJ/m) 2 ) | Coefficient of thermal conductivity (W/m.k) | |
| Example 1 | 42.41 | 2367.19 | 18.22 | 0.2422 |
| Example 3 | 44.54 | 2525.87 | 23.14 | 0.2658 |
| Comparative example 1 | 40.26 | 2068.13 | 17.32 | 0.2108 |
The imidazole ionic liquid functionalized graphene disclosed by the invention has a remarkable effect in improving the mechanical property and the heat conducting property of an ABS composite material. The 1-octyl-3-methylimidazole chloride modified graphene has a longer ball milling time, so that the structure is broken, the sheet layer is thinner, and the dispersibility and the compatibility of the graphene in ABS resin are better than those of the 1-methyl 3-butylimidazole chloride modified graphene. Therefore, the 1-octyl-3-methylimidazole chloride modified graphene is more beneficial in improving the mechanical and heat conducting properties of the ABS composite material. And the octyl chain segment is longer than the butyl chain segment, so that the 1-octyl-3-methylimidazole chloride modified graphene is more beneficial in improving the impact performance of the ABS composite material.
Claims (10)
1. The imidazole ionic liquid functionalized graphene is characterized in that the ionic liquid functionalized graphene is characterized in that imidazole groups in the imidazole ionic liquid and a six-membered ring structure of the graphene both belong to conjugated structures, pi-pi stacking interaction is generated between the imidazole groups and the six-membered ring structure of the graphene, and the ionic liquid is adsorbed on the surface of the graphene in a non-covalent bond mode.
2. The imidazole ionic liquid functionalized graphene according to claim 1, wherein the imidazole ionic liquid is one of 1-methyl 3-butyl imidazole chloride salt, 1-butyl 3-methyl imidazole chloride salt and 1-octyl-3-methyl imidazole chloride salt.
3. A method for preparing the imidazole ionic liquid functionalized graphene according to claim 1 or 2, which is characterized by comprising the following steps:
step (1): adding a solvent into the imidazole ionic liquid to obtain a mixed solution; adding graphene into a ball milling tank containing grinding balls, and then adding the mixed solution into the ball milling tank for ball milling to obtain a product;
step (2): and (3) adding the product obtained in the step (1) into an organic solvent, centrifuging, washing, drying, performing ultrasonic dispersion on the dried product, and finally drying to obtain the black powdery imidazole ionic liquid functionalized graphene.
4. The method for preparing the imidazole ionic liquid functionalized graphene according to claim 3, wherein in the step (1), the solvent is a mixture of water and one of methanol, ethanol, THF and DMF, and the mass concentration of the organic solvent in the mixture is 50%.
5. The method for preparing the imidazole ionic liquid functionalized graphene according to claim 3, wherein the dosage ratio of the imidazole ionic liquid to the solvent in the step (1) is: (1-10) g, 50mL.
6. The method for preparing imidazole ionic liquid functionalized graphene according to claim 3, wherein the graphene in the step (1) is reduced graphene oxide; the mass ratio of the graphene to the imidazole ionic liquid is 1 (1-10).
7. The method for preparing imidazole ionic liquid functionalized graphene according to claim 3, wherein the ball milling tank and the grinding balls in the step (1) are made of zirconia; the ball-material ratio of the grinding balls to the graphene and the mixed solution in the ball milling tank is (4-6): 1; the ball milling time is 3-6h, and the ball milling revolution is 100-200rpm.
8. The method for preparing imidazole ionic liquid functionalized graphene according to claim 3, wherein the organic solvent in the step (2) is one of methanol, ethanol, THF and DMF; and (3) centrifuging, wherein the centrifugal revolution is at least 10000rpm, and stopping centrifuging when all the products are accumulated at the bottom of the centrifugal tube and the upper layer of the centrifugal tube is clear liquid.
9. The method for preparing the imidazole ionic liquid functionalized graphene according to claim 3, wherein in the step (2), washing and drying are performed for 2-3 times by using an organic solvent and water alternately, and then drying is performed in an oven at 60-80 ℃ for 10-12 hours.
10. The preparation method of the imidazole ionic liquid functionalized graphene according to claim 3, wherein the ultrasonic dispersion in the step (2) is specifically carried out in water, the dispersion time is 5-10h, and the ultrasonic temperature is not more than 30 ℃; the drying mode after ultrasonic dispersion adopts freeze drying.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311310577.8A CN117303357A (en) | 2023-10-11 | 2023-10-11 | Imidazole ionic liquid functionalized graphene and preparation method thereof |
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| CN202311310577.8A CN117303357A (en) | 2023-10-11 | 2023-10-11 | Imidazole ionic liquid functionalized graphene and preparation method thereof |
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