CN111171606A - Graphene-carbon black composite granules and preparation method and application thereof - Google Patents
Graphene-carbon black composite granules and preparation method and application thereof Download PDFInfo
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- CN111171606A CN111171606A CN201911388328.4A CN201911388328A CN111171606A CN 111171606 A CN111171606 A CN 111171606A CN 201911388328 A CN201911388328 A CN 201911388328A CN 111171606 A CN111171606 A CN 111171606A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a graphene dispersion method-graphene-carbon black composite granules and a preparation method and application thereof, and relates to graphene and carbon black composite granules and a preparation method and application thereof. The preparation method mainly comprises the steps of uniformly dispersing graphene in a carbon black water dispersion liquid, mixing the graphene and the carbon black water dispersion liquid according to the mass ratio of 1: 1000-2 to form a stable graphene-carbon black composite dispersion liquid, and granulating the graphene-carbon black composite dispersion liquid at the temperature of 40-80 ℃. The problem of the application of graphene in high polymer materials which is difficult to disperse uniformly is solved. And the related process route is simple, the reaction condition is mild, the raw material source is rich, and the method is safe and environment-friendly.
Description
Technical Field
The invention relates to a preparation method and application of graphene-carbon black composite granules, and mainly relates to the field of high polymer materials.
Background
Graphene (GE) is a two-dimensional sheet structure, the basic structural unit is a sp2 hybridized hexagon composed of carbon atoms, and the thickness is a single atomic layer or multiple atomic layers. The theoretical specific surface area of GE reaches 2630m2The Young modulus is 1100GPa, the thermal conductivity is 5300W/(m.k), and the electron mobility is 15000cm2V · s. Due to the unique structural characteristics of the composite material, the composite material quickly becomes a hotspot in various research fields such as energy electronic materials and the like in the field of high polymer materials, and a plurality of researchers utilize the structural characteristics of GE to prepare the high-performance GE/high polymer material nano composite material. However, due to the extremely high chemical stability and the extremely low surface energy of graphene, the compatibility of graphene with most polymer material matrixes is poor, and the direct application of graphene in the polymer material matrix materials is limited. Therefore, how to solve the problems of uniform dispersion of graphene in the matrix and good matrix-graphene interface adhesion is the key to solve the application problem of graphene in the field of high polymer materialsWhere.
Disclosure of Invention
Based on the above problems, the present invention is to provide a method for preparing graphene-carbon black composite pellets which are stably dispersed in a polymer material and have good processability.
The technical scheme of the invention is as follows: the invention provides a preparation method of graphene-carbon black composite granules, which comprises the following steps: preparing graphene into a graphene aqueous solution with a certain concentration, then carrying out ultrasonic treatment on the graphene solution, directly adding the graphene solution into carbon black granulating water after the ultrasonic treatment, then adding a binder, strongly stirring and mixing the mixture through stirring teeth, and then obtaining composite granules through a carbon black granulator.
The graphene-carbon black composite granules are used for preparing a high polymer rubber composite material.
Compared with the prior art, the invention has the advantages that:
(1) the graphene dispersion liquid and the carbon black dispersion liquid are stirred and mixed in advance, carbon black ions are attached to the graphene nanosheets, agglomeration between graphene and graphene is avoided, the problems that the graphene is poor in dispersibility in a high polymer material and difficult to apply are solved, the obtained graphene-carbon black composite granules are good in stability and large in graphene dispersion amount, and application of the graphene in the direction of the high polymer material can be greatly promoted;
(2) the graphene and the carbon black are made into composite granules which are added into the rubber together, the repulsion between the graphene and the carbon black can be reduced by the integral addition, and the obtained graphene-carbon black composite granules are stably dispersed in a high polymer material and have good interface compatibility with the high polymer material.
(3) According to the invention, the graphene dispersion liquid is directly added in the carbon black granulation process, and the uniform compounding and the co-extrusion granulation are carried out. In the method, the rotation number of the stirring teeth, the environmental temperature of granulation, the using amount of granulation water and the using amount of a binder all have important influences on the performance of the composite granules.
(4) The method has the advantages of simple process route, mild reaction conditions and rich raw material sources, can avoid the use of volatile toxic organic solvent in the graphene dispersion process, belongs to an environment-friendly route, and is safe and environment-friendly. The method has simple equipment and process, is convenient to operate and is easy to realize large-scale industrial production.
Drawings
Fig. 1 is a TEM image of a projection electron microscope of the graphene/carbon black composite.
Fig. 2 is a TEM image of a projection electron microscope of the composite material prepared in the comparative example.
FIG. 3 is a TEM image of a projection electron microscope of the composite material prepared in the example.
Detailed Description
The present invention is further illustrated by the following specific examples and comparative examples. However, the present invention is not limited to the following.
Example 1:
the specific preparation process flow of the graphene/carbon black composite pellet related to the embodiment is as follows:
the specific implementation comprises the following steps: placing graphene in 0.5-10L of deionized water to prepare a graphene solution with the concentration of 0.5-2 mg/ml, then carrying out ultrasonic treatment on the graphene solution for 10-100 min, directly adding the graphene solution into carbon black granulation water, then adding a binder (such as plant polyphenol), wherein the using amount of the binder accounts for 3% -6% of the granulation water, intensively stirring and mixing the graphene solution and the carbon black granulation water through stirring teeth with the rotating speed controlled at 300-600 r/min, and then obtaining composite granules through a carbon black granulator, wherein the granulation environment temperature is controlled at 40-80 ℃, the outer cylinder temperature of the carbon black granulator is controlled at 70-100 ℃, and the problem of wall hanging of the graphene and the carbon black is avoided.
Comparative example 1: 0.1g of graphene, 9.9g of carbon black and 50g of natural rubber are weighed out and internally mixed in an internal mixer for 10min, and then the mixture is subjected to sheet loading and unloading in an open mill.
Example 2: 10g of graphene-carbon black composite pellets prepared according to the method of example 1 (graphene: carbon black composite ratio is 1:100) and 50g of natural rubber are weighed and banburied in an internal mixer for 10min, and then subjected to open-coupling milling for upper and lower sheets.
As shown in fig. 1, which is a TEM image of the graphene/carbon black composite prepared in example 1, the recombination interaction of graphene and carbon black inhibits the strong interaction between graphene sheets, so that graphene is not agglomerated and carbon black is uniformly and compositely distributed on the graphene sheets.
As shown in fig. 2, the graphene/carbon black composite pellet (fig. 2) prepared by the present invention is stably and uniformly dispersed in natural rubber, has no graphene agglomeration, can still be observed in a rubber matrix as a graphene sheet, and has good interfacial adhesion with a matrix material and excellent compatibility. However, the uncomplexed graphene was agglomerated in a natural rubber matrix, and no graphene flakes were observed (fig. 3).
It should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. The preparation method of the graphene/carbon black composite granules is characterized by comprising the following steps:
preparing graphene into a graphene aqueous solution with a certain concentration, then carrying out ultrasonic treatment on the graphene aqueous solution, then directly adding the graphene aqueous solution into carbon black granulation water, then adding a binder, strongly stirring and mixing through stirring teeth, and then carrying out a carbon black granulator to obtain composite granules.
2. The method for preparing the graphene/carbon black composite pellet as claimed in claim 1, wherein the concentration of the graphene aqueous solution is 0.5-2 mg/ml, and the mass ratio of graphene to carbon black is 1: 1000-2.
3. The preparation method of the graphene/carbon black composite granules according to claim 2, wherein the rotation speed of the stirring teeth is controlled to be 300-600 r/min, the granulation environment temperature is controlled to be 40-80 ℃, and the using amount of the binder accounts for 3% -6% of the granulation water.
4. The preparation method of the graphene/carbon black composite granules according to claim 2, wherein the temperature of the outer cylinder of the carbon black granulator is controlled to be 70-100 ℃.
5. A graphene/carbon black composite pellet prepared by the preparation method of claims 1 to 4.
6. Use of the graphene/carbon black composite pellet prepared according to claim 5 for preparing a polymer rubber composite.
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| CN201911388328.4A CN111171606A (en) | 2019-12-30 | 2019-12-30 | Graphene-carbon black composite granules and preparation method and application thereof |
| CN202011617269.6A CN112552712A (en) | 2019-12-30 | 2020-12-30 | Functionalized graphene-carbon black composite granules and preparation method and application thereof |
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| CN201911388328.4A CN111171606A (en) | 2019-12-30 | 2019-12-30 | Graphene-carbon black composite granules and preparation method and application thereof |
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| CN202011617269.6A Pending CN112552712A (en) | 2019-12-30 | 2020-12-30 | Functionalized graphene-carbon black composite granules and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808447A (en) * | 2020-07-22 | 2020-10-23 | 茂名环星新材料股份有限公司 | Production process and production system of low-resistance carbon black for conductive plastics |
| CN112552712A (en) * | 2019-12-30 | 2021-03-26 | 青岛科技大学 | Functionalized graphene-carbon black composite granules and preparation method and application thereof |
| CN112973633A (en) * | 2021-03-01 | 2021-06-18 | 中国科学院城市环境研究所 | Activated carbon-based material and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113024934A (en) * | 2021-04-27 | 2021-06-25 | 康泰塑胶科技集团有限公司 | High-performance gas pipe and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642198A (en) * | 2013-12-02 | 2014-03-19 | 厦门凯纳石墨烯技术有限公司 | Graphene/carbon black thermoplastic resin master batch with high dispersibility and preparation method thereof |
| CN103832997A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon black composite material, preparation method and application thereof |
| CN103833011A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon black composite material, preparation method and application thereof |
| US20140323610A1 (en) * | 2012-02-23 | 2014-10-30 | Beijing University Of Chemical Technology | Method for preparing graphene oxide/white carbon black/rubber nanocomposite material |
| CN109721812A (en) * | 2019-02-27 | 2019-05-07 | 山西永东化工股份有限公司 | The preparation method and its device of a kind of graphene/conductive black composite material and application |
| CN109880405A (en) * | 2019-04-01 | 2019-06-14 | 济南圣泉集团股份有限公司 | A kind of modified carbon black particle and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219211B (en) * | 2011-04-16 | 2015-03-11 | 华南理工大学 | Method for reducing and decorating graphene oxide by plant polyphenol and derivant thereof |
| CN103112847B (en) * | 2013-02-26 | 2014-12-03 | 华南理工大学 | Method for preparing functionalized graphene through Mannich reaction |
| CN111171606A (en) * | 2019-12-30 | 2020-05-19 | 青岛科技大学 | Graphene-carbon black composite granules and preparation method and application thereof |
-
2019
- 2019-12-30 CN CN201911388328.4A patent/CN111171606A/en active Pending
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- 2020-12-30 CN CN202011617269.6A patent/CN112552712A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140323610A1 (en) * | 2012-02-23 | 2014-10-30 | Beijing University Of Chemical Technology | Method for preparing graphene oxide/white carbon black/rubber nanocomposite material |
| CN103832997A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon black composite material, preparation method and application thereof |
| CN103833011A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/carbon black composite material, preparation method and application thereof |
| CN103642198A (en) * | 2013-12-02 | 2014-03-19 | 厦门凯纳石墨烯技术有限公司 | Graphene/carbon black thermoplastic resin master batch with high dispersibility and preparation method thereof |
| CN109721812A (en) * | 2019-02-27 | 2019-05-07 | 山西永东化工股份有限公司 | The preparation method and its device of a kind of graphene/conductive black composite material and application |
| CN109880405A (en) * | 2019-04-01 | 2019-06-14 | 济南圣泉集团股份有限公司 | A kind of modified carbon black particle and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552712A (en) * | 2019-12-30 | 2021-03-26 | 青岛科技大学 | Functionalized graphene-carbon black composite granules and preparation method and application thereof |
| CN111808447A (en) * | 2020-07-22 | 2020-10-23 | 茂名环星新材料股份有限公司 | Production process and production system of low-resistance carbon black for conductive plastics |
| CN112973633A (en) * | 2021-03-01 | 2021-06-18 | 中国科学院城市环境研究所 | Activated carbon-based material and preparation method and application thereof |
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Application publication date: 20200519 |