CN111099579A - Preparation method of water-dispersible carbon material - Google Patents
Preparation method of water-dispersible carbon material Download PDFInfo
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- CN111099579A CN111099579A CN201811247057.6A CN201811247057A CN111099579A CN 111099579 A CN111099579 A CN 111099579A CN 201811247057 A CN201811247057 A CN 201811247057A CN 111099579 A CN111099579 A CN 111099579A
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Abstract
The invention provides a preparation method of a water-dispersible carbon material. Adding olefin with high activity and hydrophilic functional groups and a catalyst into a carbon material system through Diels-Alder reaction or free radical addition reaction to obtain a carbon material introduced with the hydrophilic functional group olefin; and then stripping the carbon material introduced with the hydrophilic functional group olefin by using ultrasound, high shear, a nano grinder and a nano homogenizer, and then carrying out solid-liquid separation and drying to obtain water-dispersible carbon material powder. The carbon material prepared by the method has good water dispersibility, and can be stably dispersed in water for a long time; meanwhile, the preparation method of the carbon material is convenient, simple, low in cost, environment-friendly, wide in application range and easy to realize industrialization.
Description
Technical Field
The invention relates to the field of modified carbon materials, and particularly relates to a preparation method of a water-dispersible carbon material.
Background
Graphene is a two-dimensional honeycomb material formed by tightly stacking single-layer-thickness carbon atoms. Graphene has been the focus of research in various fields due to its excellent physicochemical properties, such as high specific surface area, excellent mechanical, electrical, magnetic, thermal and optical properties. With the continuous and intensive research on graphene, the problem of compatibility between graphene and other materials is more and more emphasized, so that the preparation of water-dispersible graphene becomes an important research topic.
Inorganic materials (including carbon material graphite, graphene, carbon nano tube and fullerene) need to be well dispersed in water, the surface of the inorganic materials needs to have a certain hydrophilic matrix, such as carboxyl, hydroxyl and the like, and graphene oxide can be dispersed in water mainly because the structure of the graphene oxide has a large number of hydrophilic groups: carboxyl, hydroxyl, epoxy, and the like, high quality graphene cannot be dispersed in water because there is no hydrophilic group.
Graphene is high in chemical stability, and van der waals force exists between sheets, so that graphene is easy to agglomerate and is difficult to disperse in water. Graphene produced in the prior art is difficult to realize sufficient and stable dispersion in water, which greatly hinders further research and development of graphene, thereby limiting the application range of graphene. How to solve the problem of the dispersibility of graphene in water is the difficulty and the key for obtaining the water-dispersible graphene. The solution is that graphene is modified usually, but the graphene has stable chemical properties, and a large amount of strong acid and strong oxidant are required to be used for oxidizing the graphene (such as graphene oxide) in order to modify the graphene, and then the oxidized graphene is subjected to graft modification through a chemical reaction. However, oxidation of graphene by strong acid and strong oxidant not only destroys the structure of graphene but also reduces its performance, and meanwhile, strong acid and strong oxidant cause great environmental pollution, and a great deal of manpower and material resources are spent on post-treatment. The large conjugated structure of the prepared graphene oxide is seriously damaged, even a cavity appears in a sheet layer, and the structure of the graphene oxide has a large number of hydrophilic groups: the reduced graphene oxide is obtained by hydrogenation reduction on the basis of graphene oxide, and mainly removes hydroxyl and epoxy, so that carboxyl cannot be removed, and a conjugated structure is difficult to repair.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a water-dispersible carbon material, which comprises the following steps:
step 1: adding olefin with high activity and hydrophilic functional groups, a catalyst and a carbon material into N, N-dimethylformamide through Diels-Alder reaction or free radical addition reaction, and reacting at 75-150 ℃ for 18-30 hours to obtain the carbon material introduced with the hydrophilic functional group olefin;
step 2: sequentially subjecting the carbon material introduced with the hydrophilic functional group olefin obtained in the step 1 to ultrasonic treatment, high shear treatment, a nano grinder and a nano homogenizer for stripping for 0.5-4 hours, performing solid-liquid separation, and drying at 50 ℃ to obtain water-dispersible carbon material powder;
wherein: the carbon material includes graphite, graphene, carbon nanotubes and fullerenes; the graphene comprises reduced graphene oxide;
the alkene with the hydrophilic functional group comprises any one of acrylic acid, crotonic acid, ethyl crotonate, itaconic acid, itaconic anhydride, methyl itaconate, ethyl itaconate or cinnamic acid or any combination thereof;
when the catalyst is subjected to Diels-Alder reaction, the catalyst is any one or any combination of the following (I) to (IV):
(I)
wherein R is1＝CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3Or C (CH)3)3
(II)
Wherein R is2＝CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3Or C (CH)3)3
(III)
Wherein R is3＝CH3Br or Cl
(IV)
Wherein R is4＝CH3Br or Cl
When reacting by free radical addition, the catalyst comprises any one or any combination of diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, cyclohexanone peroxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, potassium persulfate, sodium persulfate or ammonium persulfate;
the mass ratio of the catalyst, the olefin with the hydrophilic functional group and the carbon material is as follows: the catalyst, the olefin having a hydrophilic functional group and the carbon material are (0.5-5), (2-30) and (60-92).
Compared with the prior art, the invention has the beneficial effects that:
(1) the water-dispersible carbon material prepared by the method has excellent water dispersibility and wide application range. The water-dispersible graphene is different from the traditional graphene, can be fully and stably dispersed in water under the condition of keeping the large conjugated structure of the graphene, solves the problem of poor compatibility with other materials due to the inherent hydrophobicity of the traditional graphene, and greatly expands the application range of the graphene.
(2) The preparation method for modifying the carbon material by modifying the hydrophilic functional group on the surface of the carbon material can be carried out on the existing industrial equipment, has the advantages of simple, quick and environment-friendly method, easy operation, industrialization and the like in the preparation process, and can obtain a large amount of water-dispersible carbon material at one time.
Drawings
FIG. 1 is a structural diagram of a water-dispersible carbon material provided in example 2 of the present application.
Fig. 2 is a transmission electron microscope image of the water-dispersible carbon material provided in example 2 of the present application.
FIG. 3 is an atomic force microscope scan of a water-dispersible carbon material provided in example 2 of the present application.
Fig. 4 is a height map (i.e., graphene thickness) of the graphene sheet at the mark of fig. 3.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Examples 1 to 5
The preparation method of embodiments 1 to 5, comprising the steps of:
step 1: adding olefin with high activity and hydrophilic functional groups, a catalyst and a carbon material into N, N-dimethylformamide through a Diels-Alder reaction, and reacting at 75-150 ℃ for 18-30 hours to obtain the carbon material introduced with the hydrophilic functional group olefin;
step 2: and (2) sequentially subjecting the carbon material introduced with the hydrophilic functional group olefin obtained in the step (1) to ultrasonic treatment, high shear treatment, nano grinding machine and nano homogenizer for stripping for 0.5-4 hours, performing solid-liquid separation, and drying at 50 ℃ to obtain water-dispersible carbon material powder.
The raw materials and experimental conditions used are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
Examples 6 to 10
The preparation method of embodiment 6 to 10, comprising the steps of:
step 1: adding olefin with high activity and hydrophilic functional groups, a catalyst and a carbon material into N, N-dimethylformamide through free radical addition reaction, and reacting at 75-150 ℃ for 18-30 hours to obtain the carbon material with the hydrophilic functional group-introduced olefin;
step 2: and (2) sequentially subjecting the carbon material introduced with the hydrophilic functional group olefin obtained in the step (1) to ultrasonic treatment, high shear treatment, nano grinding machine and nano homogenizer for stripping for 0.5-4 hours, performing solid-liquid separation, and drying at 50 ℃ to obtain water-dispersible carbon material powder.
The raw materials and experimental conditions used are shown in tables 3 and 4, respectively.
TABLE 3
TABLE 4
The settling properties of the carbon materials obtained in the examples are shown in Table 5. As can be seen from Table 5, the water-dispersible carbon material prepared by the method of the present invention can maintain good water dispersibility after 72 hours of sedimentation test, and has no obvious sedimentation or only little sedimentation.
TABLE 5
| Examples | Concentration of the dispersion | Settling property for 24h | Settling property for 72h |
| Example 1 | 0.1mg/mL | Without obvious settlement | Small amount of sedimentation |
| Example 2 | 0.1mg/mL | Small amount of sedimentation | Small amount of sedimentation |
| Example 3 | 0.1mg/mL | Without obvious settlement | Without obvious settlement |
| Example 4 | 0.1mg/mL | Without obvious settlement | Without obvious settlement |
| Example 5 | 0.1mg/mL | Without obvious settlement | Without obvious settlement |
| Example 6 | 0.1mg/mL | Without obvious settlement | Without obvious settlement |
| Example 7 | 0.1mg/mL | Small amount of sedimentation | Small amount of sedimentation |
| Example 8 | 0.1mg/mL | Without obvious settlement | Without obvious settlement |
| Example 9 | 0.1mg/mL | Without obvious settlement | Without obvious settlement |
| Example 10 | 0.1mg/mL | Without obvious settlement | Small amount of sedimentation |
Claims (7)
1. A method for producing a water-dispersible carbon material, comprising the steps of:
step 1: adding olefin with high activity and hydrophilic functional groups, a catalyst and a carbon material into N, N-dimethylformamide through Diels-Alder reaction or free radical addition reaction, and reacting at 75-150 ℃ for 18-30 hours to obtain the carbon material introduced with the hydrophilic functional group olefin;
step 2: and (2) sequentially subjecting the carbon material introduced with the hydrophilic functional group olefin obtained in the step (1) to ultrasonic treatment, high shear treatment, nano grinding machine and nano homogenizer for stripping for 0.5-4 hours, performing solid-liquid separation, and drying at 50 ℃ to obtain water-dispersible carbon material powder.
2. The method for producing a water-dispersible carbon material according to claim 1, wherein the carbon material comprises graphite, graphene, carbon nanotubes, and fullerene.
3. The method of claim 1, wherein the olefin having a hydrophilic functional group comprises any one or any combination of acrylic acid, crotonic acid ethyl ester, itaconic acid, itaconic anhydride, itaconic acid methyl ester, itaconic acid ethyl ester, or cinnamic acid.
4. The method for producing a water-dispersible carbon material according to claim 1, wherein the catalyst is any one or any combination of the following (I) to (IV) when subjected to a Diels-Alder reaction:
(I)
wherein R is1＝CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3Or C (CH)3)3
(II)
Wherein R is2＝CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3Or C (CH)3)3(III)
Wherein R is3＝CH3Br or Cl
(IV)
Wherein R is4＝CH3Br or Cl.
5. The method for producing a water-dispersible carbon material according to claim 1, wherein the catalyst comprises any one of diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, cyclohexanone peroxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, potassium persulfate, sodium persulfate, or ammonium persulfate, or any combination thereof, when reacted by radical addition.
6. The method for producing a water-dispersible carbon material according to claim 1, wherein the catalyst, the olefin having a hydrophilic functional group, and the carbon material are present in a mass ratio of: the catalyst, the olefin having a hydrophilic functional group and the carbon material are (0.5-5), (2-30) and (60-92).
7. The method for producing a water-dispersible carbon material according to claim 1, wherein the graphene comprises reduced graphene oxide.
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Citations (7)
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| JP2007169112A (en) * | 2005-12-22 | 2007-07-05 | Tokyo Univ Of Science | Modified carbon material and method for producing the same |
| US20080160308A1 (en) * | 2003-06-27 | 2008-07-03 | Industrial Technology Research Institute | Organically functionalized carbon nanocapsule |
| US20130331501A1 (en) * | 2009-04-01 | 2013-12-12 | Cal Poly Corporation | Isolation of carbon nanotubes by chemical functionalization |
| US20140080950A1 (en) * | 2011-11-30 | 2014-03-20 | Niigata University | Functional-group-modified carbon material, and method for producing same |
| US20150112066A1 (en) * | 2012-06-11 | 2015-04-23 | New York University | Asymmetric catalysts |
| US20160280545A1 (en) * | 2013-11-14 | 2016-09-29 | Imperial Innovations Limited | Preparation of functionalised carbon nanomaterials |
| CN108675286A (en) * | 2018-07-11 | 2018-10-19 | 天津工业大学 | The method that efficiently stripping graphite powder prepares functionalization graphene |
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2018
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080160308A1 (en) * | 2003-06-27 | 2008-07-03 | Industrial Technology Research Institute | Organically functionalized carbon nanocapsule |
| JP2007169112A (en) * | 2005-12-22 | 2007-07-05 | Tokyo Univ Of Science | Modified carbon material and method for producing the same |
| US20130331501A1 (en) * | 2009-04-01 | 2013-12-12 | Cal Poly Corporation | Isolation of carbon nanotubes by chemical functionalization |
| US20140080950A1 (en) * | 2011-11-30 | 2014-03-20 | Niigata University | Functional-group-modified carbon material, and method for producing same |
| US20150112066A1 (en) * | 2012-06-11 | 2015-04-23 | New York University | Asymmetric catalysts |
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