CN109337730A - Modified graphene and its preparation method and application - Google Patents
Modified graphene and its preparation method and application Download PDFInfo
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- CN109337730A CN109337730A CN201811239446.4A CN201811239446A CN109337730A CN 109337730 A CN109337730 A CN 109337730A CN 201811239446 A CN201811239446 A CN 201811239446A CN 109337730 A CN109337730 A CN 109337730A
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- modified graphene
- preparation
- mixed liquor
- ultrasound
- graphite oxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
Abstract
The present invention relates to a kind of modified graphenes and its preparation method and application.The preparation method of the modified graphene includes that step includes: to mix graphite oxide with water, highly basic, obtains mixed liquor, and wherein the mass ratio of graphite oxide and water is 1:500~2000, and the concentration of highly basic is 0.3mg/mL~1.0mg/mL in mixed liquor；And by mixed liquor ultrasound, obtain modified graphene.Preparation method is simple for above-mentioned modified graphene, and reaction condition is mild, and product is nontoxic and environmental-friendly.It is verified, there is good dissolubility and dispersibility in organic solvent according to the modified graphene that above-mentioned preparation method is prepared.
Description
Technical field
The present invention relates to technical field of graphene, more particularly to a kind of modified graphene and its preparation method and application.
Background technique
Nano material graphene with unique two-dimensional structure makes it have excellent electronics electric property, superpower because of it
Mechanical strength and good heat conductivity are all widely used in many fields, for example, sensor, composite material etc.
Deng.
Preparing the main method of graphene at present is so that it is changed into graphite by reduction using graphene oxide as presoma
Alkene.The restoring method used at present mainly has a chemical reagent reduction, hot solution reduction method etc., and hydrazine and its derivative (hydrazine hydrate, two
Methyl hydrazine) as a kind of liquid reduction reagent be a kind of reagent for being commonly used to prepare redox graphene, due to hydrazine and its
Derivative has severe toxicity, therefore limits the practicality.And the graphene of traditional method preparation is in the dissolution of organic solvent
Degree is smaller, affects further applying for it.
Summary of the invention
Based on this, it is necessary to provide the preparation method of a kind of polymolecularity and the modified graphene of highly dissoluble.
In addition, also providing a kind of with polymolecularity, the modified graphene of high-dissolvability and its application.
A kind of preparation method of modified graphene, comprising the following steps:
Graphite oxide is mixed with water, highly basic, obtains mixed liquor, wherein the mass ratio of the graphite oxide and water is 1:
500~2000, the concentration of highly basic described in the mixed liquor is 0.3mg/mL~1.0mg/mL；And
By the mixed liquor ultrasound, the modified graphene is obtained.
Preparation method is simple for above-mentioned modified graphene, and reaction condition is mild, and product is nontoxic and environmental-friendly, Yi Shi
Now produce in batches.In addition, it turned out that, the modified graphene being prepared according to above-mentioned preparation method has good in organic solvent
Good dissolubility and dispersibility.
The highly basic is in sodium hydroxide, potassium hydroxide, potassium tert-butoxide and barium hydroxide in one of the embodiments,
At least one.
In one of the embodiments, in the step of the mixed liquor ultrasound, the power of the ultrasound be 180W~
360W。
It further include by the mixing before in one of the embodiments, described by the step of the mixed liquor ultrasound
The step of liquid flows back.
The time of the reflux is 0.8h~2h in one of the embodiments,.
The step by the mixed liquor ultrasound includes: and obtains the mixed liquor ultrasound in one of the embodiments,
To ultrasonic liquid；And the ultrasonic liquid is centrifuged.
In one of the embodiments, in described the step of being centrifuged the ultrasonic liquid, the revolving speed of the centrifugation is
10000r/min~15000r/min, the time of the centrifugation are 30min~90min.
The partial size of the graphite oxide is 50nm~150nm in one of the embodiments,.
A kind of modified graphene is made by the preparation method of above-mentioned modified graphene.
Above-mentioned modified graphene is preparing the application in lubricating oil.
Detailed description of the invention
Fig. 1 is the dissolution degree result figure of embodiment 1；
Fig. 2 is that the SEM of embodiment 2 schemes；
Fig. 3 is that the SEM of embodiment 3 schemes.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give section Example of the invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the disclosure of invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The preparation method of the modified graphene of one embodiment, comprising the following steps:
S110, graphite oxide is mixed with water, highly basic, obtains mixed liquor.
Specifically, graphite oxide is mixed with water, highly basic, obtains mixed liquor.Wherein, the mass ratio of graphite oxide and water is
1:500~2000, the concentration of highly basic is 0.3mg/ml~1.0mg/ml in mixed liquor.
First graphite oxide is mixed with water in one of the embodiments, is then mixed again with highly basic, mixed liquor is obtained.
The partial size of graphite oxide is 50nm~150nm in one of the embodiments,.Further, the grain of graphite oxide
Diameter is 80nm~120nm, still further, the partial size of graphite oxide is 90nm~110nm.Further, graphite oxide
Partial size is 100nm.
Water is deionized water in one of the embodiments,.
The mass ratio of graphite oxide and water is 1:1000~1800 in one of the embodiments,.Further, stone is aoxidized
The mass ratio of ink and water is 1:1200~1600.Further, the mass ratio of graphite oxide and water be 1:1300,1:1350,
1:1400,1:1450,1:1500 or 1:1550.
Highly basic is selected from sodium hydroxide (NaOH), potassium hydroxide (KOH), potassium tert-butoxide (t- in one of the embodiments,
) and barium hydroxide (Ba (OH) BuOK2At least one of).Further, highly basic is sodium hydroxide.
The concentration of highly basic is 0.3mg/mL~1.0mg/mL in mixed liquor in one of the embodiments,.Further, it mixes
The concentration for closing highly basic in liquid is 0.4mg/mL~0.8mg/mL.Still further, the concentration of highly basic is 0.5mg/mL in mixed liquor
~0.7mg/mL.Further, in mixed liquor highly basic concentration be 0.5mg/mL, 0.55mg/mL, 0.6mg/mL or
0.65mg/mL。
The concentration of NaOH is 0.3mg/mL~1.0mg/mL in mixed liquor in one of the embodiments,.In mixed liquor
The concentration of NaOH is 0.4mg/mL~0.8mg/mL.Still further, in mixed liquor NaOH concentration be 0.5mg/mL~
0.7mg/mL.Further, the concentration of NaOH is 0.5mg/mL, 0.55mg/mL, 0.6mg/mL or 0.65mg/ in mixed liquor
mL。
S130, mixed liquor is flowed back, obtains phegma.
Specifically, mixed liquor is flowed back under stiring, obtains phegma.
The time flowed back in one of the embodiments, is 0.8h~2h.Further, the time of reflux be 0.8h~
1.5h.Further, the time of reflux is 1h~1.2h.
In one of the embodiments, further, the rate of stirring is 500 revolutions per seconds.
Mixed liquor reflux is conducive to improve modified graphene solubility in organic solvent, has it in organic solution
There is better dispersibility.It is understood that in wherein some embodiments, the step of reflux, be can be omitted, at this point, directly
Mixed liquor is subjected to next step operation.
S150, by phegma ultrasound, obtain modified graphene.
Ultrasonic power is 180W~360W in one of the embodiments,.Further, ultrasonic power be 200W~
260W.Further, ultrasonic power is 240W.
The ultrasonic time is 60min~200min in one of the embodiments,.Further, the ultrasonic time is
100min~200min.Further, the ultrasonic time is 150min.
First phegma ultrasound is obtained ultrasonic liquid, is then centrifuged ultrasonic liquid, changed in one of the embodiments,
Property graphene.
The revolving speed being centrifuged in one of the embodiments, is 10000r/min~15000r/min.Further, centrifugation
Revolving speed is 12000r/min~14000r/min.Further, the revolving speed of centrifugation is 13500r/min
The time being centrifuged in one of the embodiments, is 30min~90min.Further, the time of centrifugation is
30min, 40min, 60min or 90min.
The modified graphene of available size uniformity is centrifuged after ultrasound.It is understood that can according to actual needs,
The revolving speed of centrifugation is adjusted to prepare the modified graphene of different-grain diameter, realizes that the modified graphene size being prepared is controllable.
Further include the steps that washing after centrifugation in one of the embodiments,.Specifically, make to be rinsed with water centrifugation
Precipitating afterwards, and filter, obtain modified graphene.Further, water is deionized water.
In one of the embodiments, after the step of washing, include the steps that dry.
Preparation method is simple for above-mentioned modified graphene, and reaction condition is mild, and product is nontoxic and environmental-friendly, Yi Shi
Now produce in batches.
The modified graphene of one embodiment is made by the preparation method of above-mentioned modified graphene.
Verified, above-mentioned modified graphene obtains after being handled by graphite oxide through highly basic, has in organic solvent good
Dissolubility well, dispersibility.In addition, above-mentioned modified graphene also has the property similar to reproducibility, but its degree of oxidation ratio
Reduced graphene wants high.
Above-mentioned modified graphene is in preparing lubricating oil as the application in additive.
Above-mentioned modified graphene has good dissolubility and dispersibility in organic solvent, especially in N, N- dimethyl
Dissolubility in formamide (DMF), carbon tetrachloride (CCl4) is preferable, can be used as additive application in the preparation of lubricating oil.
Specific embodiment
It is described in detail below in conjunction with specific embodiment.
Following embodiment such as non-specified otherwise, then do not include the other components in addition to inevitable impurity.In embodiment
It if not otherwise indicated using drug and instrument, is this field conventional selection.The experiment side of actual conditions is not specified in embodiment
Method, according to normal conditions, such as the method that condition described in document, books or manufacturer are recommended is realized.
Embodiment 1~19
(1) each component of embodiment 1~19 is weighed according to table 1, wherein the partial size of graphite oxide (nanometer pioneer) is
100nm.Number in table 1 refers to mass fraction.
Table 1
(2) graphite oxide of each embodiment, deionized water and NaOH are mixed, obtains the mixed liquor of each embodiment.
(3) mixed liquor of each embodiment is stirred at reflux according to the corresponding counterflow condition of table 1 respectively, the speed of stirring is
500 revolutions per seconds, obtain the phegma of each embodiment.
(4) phegma of each embodiment is obtained into the ultrasound of each embodiment respectively according to the corresponding ultrasound condition ultrasound of table 1
Liquid.
(5) the ultrasonic liquid of each embodiment is centrifuged according to the corresponding centrifugal condition of table 1 respectively, then uses deionized water
Precipitating obtained by each embodiment centrifugation is rinsed respectively, then filters respectively, is dry, obtaining the modified graphene of each embodiment.
(6) dissolubility of each obtained modified graphene of embodiment is examined.Specifically, the modification that Example 1 obtains
Graphene 10mg respectively with the n,N-Dimethylformamide of 20mL (DMF), DMSO, N-Methyl pyrrolidone (NMP), ortho-xylene
(o-xylene), methylene chloride (DCM), tetrahydrofuran (THF), ethylene glycol (ethylene glycol), normal propyl alcohol (1-
Propanol), acetone (acetone), chloroform (CHCl3), methanol (methanol), carbon tetrachloride (CCl4) and ethyl alcohol it is mixed
It closes.Stand 24 hours.As a result as shown in Figure 1, wherein first row is from left to right followed successively by the modified graphene of embodiment 1 in Fig. 1
In n,N-Dimethylformamide (DMF), DMSO, N-Methyl pyrrolidone (NMP) and ortho-xylene (o-xylene)；Second row from
It is left-to-right to be followed successively by methylene chloride (DCM), tetrahydrofuran (THF), ethylene glycol (ethylene glycol) and normal propyl alcohol (1-
propanol)；Third row is from left to right followed successively by acetone (acetone), chloroform (CHCl3), methanol (methanol), four
Chlorination carbon (CCl4) and ethyl alcohol dissolved state.
(7) dispersibility for the modified graphene that each embodiment obtains is detected with scanning electron microscope (SEM).Wherein,
Fig. 2~3 are respectively the SEM figure of embodiment 1 and embodiment 2.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of modified graphene, which comprises the following steps:
Graphite oxide is mixed with water, highly basic, obtains mixed liquor, wherein the mass ratio of the graphite oxide and water be 1:500~
2000, the concentration of highly basic described in the mixed liquor is 0.3mg/mL~1.0mg/mL；And
By the mixed liquor ultrasound, the modified graphene is obtained.
2. the preparation method of modified graphene according to claim 1, which is characterized in that the highly basic is selected from hydroxide
At least one of sodium, potassium hydroxide, potassium tert-butoxide and barium hydroxide.
3. the preparation method of modified graphene according to claim 1, which is characterized in that in the step of the mixed liquor ultrasound
In rapid, the power of the ultrasound is 180W~360W.
4. the preparation method of modified graphene according to claim 1, which is characterized in that surpass the mixed liquor described
Before the step of sound, further include the steps that flowing back the mixed liquor.
5. the preparation method of modified graphene according to claim 4, which is characterized in that the time of the reflux is 0.8h
~2h.
6. the preparation method of modified graphene according to claim 1, which is characterized in that described by the mixed liquor ultrasound
The step of include:
By the mixed liquor ultrasound, ultrasonic liquid is obtained；And
The ultrasonic liquid is centrifuged.
7. the preparation method of modified graphene according to claim 6, which is characterized in that described to be centrifuged the ultrasonic liquid
The step of in, the revolving speed of the centrifugation is 10000r/min~15000r/min, and the time of the centrifugation is 30min~90min.
8. the preparation method of modified graphene according to claim 1, which is characterized in that the partial size of the graphite oxide is
50nm~150nm.
9. a kind of modified graphene, which is characterized in that by the preparation side of modified graphene according to any one of claims 1 to 8
Method is made.
10. modified graphene as claimed in claim 9 is preparing the application in lubricating oil.
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| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN104071784A (en) * | 2014-07-10 | 2014-10-01 | 中南林业科技大学 | Method for preparing graphene through reduction of oxidized graphene |
| CN104649255A (en) * | 2014-12-11 | 2015-05-27 | 宋鹏 | Method for preparing graphene through ball mill aided oxidation and reduction |
| US20160347617A1 (en) * | 2013-12-31 | 2016-12-01 | Shenzhen Cantonnet Energy Services Co. , Ltd. | A preparation method of graphene as well as graphene oxide based on anthracite |
| CN107090325A (en) * | 2017-04-28 | 2017-08-25 | 杭州高烯科技有限公司 | A kind of graphene-based lubricating oil and preparation method thereof |
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2018
- 2018-10-23 CN CN201811239446.4A patent/CN109337730B/en active Active
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| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| US20160347617A1 (en) * | 2013-12-31 | 2016-12-01 | Shenzhen Cantonnet Energy Services Co. , Ltd. | A preparation method of graphene as well as graphene oxide based on anthracite |
| CN104071784A (en) * | 2014-07-10 | 2014-10-01 | 中南林业科技大学 | Method for preparing graphene through reduction of oxidized graphene |
| CN104649255A (en) * | 2014-12-11 | 2015-05-27 | 宋鹏 | Method for preparing graphene through ball mill aided oxidation and reduction |
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