CN108862264A - A kind of graphene dispersion agent and preparation method thereof, application - Google Patents
A kind of graphene dispersion agent and preparation method thereof, application Download PDFInfo
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- CN108862264A CN108862264A CN201810822665.9A CN201810822665A CN108862264A CN 108862264 A CN108862264 A CN 108862264A CN 201810822665 A CN201810822665 A CN 201810822665A CN 108862264 A CN108862264 A CN 108862264A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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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
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Abstract
The present invention relates to field of graphene, a kind of graphene dispersion agent and preparation method thereof, application are disclosed.Graphene dispersion agent of the invention can promote graphene dispersion, and dispersion performance is good, and its can with acid react generate salt, after removing, can dilute acid wash be easy removing dispersing agent, avoid influence of the dispersing agent to graphene performance.
Description
Technical field
The present invention relates to field of graphene more particularly to a kind of graphene dispersion agent and preparation method thereof, application.
Background technique
Graphene is the carbon that monoatomic layer thickness bi-dimensional cellular shape lattice structure is interconnected to form by Sp2 hydbridized carbon atoms
Material.Graphene have excellent electricity, mechanics, calorifics and mechanical performance, be expected to transparent conductive film, composite material, the energy,
It is used widely in the fields such as sensor, biotechnology, catalysis material.
In the prior art, the preparation method of graphene includes mechanical stripping, epitaxial growth, chemical vapor deposition, oxidation
One reduction, the removing of liquid ultrasonic wave etc..Wherein, mechanical stripping, epitaxial growth, chemical vapor deposition the available defect of method
The low graphene of content, but these three methods all can only obtain a small amount of product, it is impossible to be used in largely prepare graphene.Aoxidize stone
The graphene that the method that black alkene one restores can largely prepare graphene in the solution, but obtain contains a large amount of defect and miscellaneous
Atom has damaged the mechanics of graphene, electrical and mechanical property.Liquid ultrasonic wave stripping means is by being ultrasonically treated graphite
Alkene is stripped down from graphite, and under the auxiliary of dispersing agent by graphene dispersion in the solution.This method low in raw material price,
Obtained graphene defect content is low, and can largely prepare, and is the effective ways that inexpensively can largely prepare graphene.
Existing graphene dispersion agent includes：Neopelex (SDBS), Arabic gum, polyethylene adjoin pyrrolidone
(PVP) etc., there are also the complicated organic molecules of synthesis.But these graphene dispersion agent dispersed graphite alkene in aqueous solution
Ability it is very limited, after ultrasound removing, graphene concentration is low in obtained solution, and dispersion performance is bad.
In addition, dispersing agent remains the electricity and heat performance for often also influencing graphene in graphene product.Therefore, it opens
It sends out graphene dispersion agent efficient, and is easy to remove after distribution, be the new challenge that liquid graphite removing prepares graphene.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of asymmetric 3,4,9,10- with polyether group
Graphene dispersion agent of the sub- amide of tetracarboxylic acid two and preparation method thereof, application.Graphene dispersion agent of the invention also has tertiary amine
There is group very strong lipophilicity can promote graphene dispersion, and dispersion performance is good, and after removing, can use Diluted Acid Washing
It washs and is easy to remove excess disperse agent, avoid influence of the excessive dispersing agent to graphene performance.
The specific technical solution of the present invention is：A kind of graphene dispersion agent, chemical structural formula (A) are as follows：
Wherein, R1, R2For the alkyl of C1 to C4；N=2 or 3 or 4 or 5 or 6；The alkyl of m=3~20, R3=hydrogen or C1 to C4, R
For hydrogen or the alkyl of C1 to C18.
Pi-electron and the sp2 structure of graphene surface be capable of forming very strong π-π and interact, it is big with dendroid
- the 3 of molecular radical, the sub- amide of 4,9,10- tetracarboxylic acid two are that one kind can be used for graphene dispersion and the special surface of removing is living
Property agent.But the sub- amide synthesis of existing 3,4,9, the 10- tetracarboxylic acid two with dendritic macromole group is difficult.Of the invention
Graphene dispersion agent has the basic structure of the sub- amide of 3,4,9,10- tetracarboxylic acid two, is readily synthesized, and point for graphene
Scattered and removing has the effect of outstanding.
The preparation method of above-mentioned graphene dispersion agent, includes the following steps：
1) 3, the synthesis of 4,9,10- tetrabasic carboxylic acids-monoester anhydride-ω-hydroxyethyl amide：3,4,9,10- tetracarboxylic acid dianhydrides,
In dense potassium hydroxide aqueous solution, 90 DEG C, hydrolyzable, then adjusted pH to faintly acid with concentrated hydrochloric acid, obtain 3,4,9,10- tetra-
Formic acid-monoester anhydride-monopotassium salt；3 obtained, 4,9,10- tetracarboxylic acids-monoester anhydride-monopotassium salt and in water phase and 2- amino second
Alcohol, 90 DEG C of reactions, then acid out, obtain 3,4,9,10- tetracarboxylic acids-monoester anhydride-ω-hydroxyethyl amide.
2) synthesis of 3,4,9,10- tetracarboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl amide：It will step
Rapid 1) resulting 3,4,9,10- tetracarboxylic acids-monoester anhydride-ω-hydroxyethyl amide is in DMF solvent and excessive 3- diethyl
Amino propylamine reacts to obtain as follows 3,4,9,10- tetracarboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl
Amide.
3) by resulting 3,4,9,10- tetracarboxylic acid-N, N diethyl amino propyl amide-ω of step 2)-hydroxyethyl acyl
Amine and excessive propylene oxide polymerize under potassium hydroxide catalysed, control reaction condition, obtain average molecular weight in 700-1700
Graphene dispersion agent (D).
Preferably, the average molecular weight of the resulting graphene dispersion agent (D) of step 3) is 700-1700.
Application of the above-mentioned graphene dispersion agent in graphene preparation, includes the following steps：By graphite, graphene dispersion
Agent, distilled water and zirconium pearl, which are added in container, to be mixed, and ultrasonic removing is carried out under ultrasonic wave auxiliary；After removing, by zirconium pearl
Separation, centrifuge separation, takes graphene upper clear liquid.
Zirconium pearl is added during liquid ultrasonic wave removes graphite in the present invention in graphite dispersing solution, can be effectively
Improve the charge stripping efficiency of graphite.But since graphene itself is not soluble in water, in the case where lacking dispersant with high efficiency, removing
Limitation, obtained graphene concentration are lower (0.04mg/mL or so).And after being added to graphene dispersion agent of the invention,
The removing of graphite can further be promoted, improve the disperse properties of graphene in water, prevent reassembling for graphene.It is obtained
Graphene concentration it is higher (2.0mg/mL or so), thinner thickness (is smaller than 3nm).
Preferably, the graphite, graphene dispersion agent, distilled water and the mass ratio of zirconium pearl are 1: 0.01-0.5: 20-
200∶20-500。
Preferably, the partial size of the zirconium pearl is 0.2-1.5mm.
Preferably, ultrasonic wave unit power (ultrasonic power/1 gram graphene) is 20-200 watts/gram, splitting time is
10-20h。
Preferably, the revolving speed of centrifuge separation is 1000-10000rpm.
It is compared with the prior art, the beneficial effects of the invention are as follows：
1, graphene dispersion agent of the invention has excellent graphene dispersion ability, the graphene prepared by ultrasonic method,
Defect is few, and preparation method is simple, and it can be more than 2mg/ml that the concentration of the aqueous dispersions of graphene is high.
2, graphene dispersion agent of the invention can react into salt with acid, therefore can use Diluted Acid Washing after graphite removing
It washs and is easy to remove dispersing agent, avoid influence of the excess disperse agent to graphene performance.
Detailed description of the invention
Fig. 1 is the AFM test result figure of graphene made from embodiment 3；
Fig. 2 is 4,9,10- tetracarboxylic acids-monoester anhydride-monopotassium salt (E) IR (KBr) test chart -3 made from embodiment 1；
Fig. 3 is 3 made from embodiment 1, and 4,9,10- tetrabasic carboxylic acids-monoester anhydride-ω-hydroxyethyl amide (B) IR (KBr) is surveyed
Attempt；
Fig. 4 is 3,4,9,10- tetrabasic carboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl amide made from embodiment 1
(F) IR test chart.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1 (graphene dispersion agent preparation)
A kind of graphene dispersion agent, chemical structural formula (D) are as follows：
Wherein, R1, R2For the alkyl of C1 to C4；N=2 or 3 or 4 or 5 or 6.
The preparation method of above-mentioned graphene dispersion agent, includes the following steps：
1) 3, the synthesis of 4,9,10- tetrabasic carboxylic acids-monoester anhydride-ω-hydroxyethyl amide：Thermometer, blender, nitrogen are being housed
Ingress pipe, addition funnel add 3,4,9, the 10- tetracarboxylic acid dianhydrides of 19.6g, the distillation of 200ml in the reaction flask of return pipe
Water, 85% potassium hydroxide of 13.29g, nitrogen import, and stirring is warming up to 90 DEG C, pH is adjusted to 10~11, about in 2 hours
31% hydrochloric acid of 18.0g is added dropwise.PH is adjusted to 4.5~5.0 again, continues to react 1 hour at 90 DEG C, filter while hot, 5L is warm
Water washing, 80 DEG C of dryings obtain-the 3 of 21.4g, 4,9,10- tetracarboxylic acids-monoester anhydride-monopotassium salt (E).IR (KBr) is measured such as
Shown in Fig. 2.
Thermometer is being housed, blender, nitrogen ingress pipe, addition funnel adds the distillation of 100ml in the reaction flask of return pipe
Water, the 2- ethylaminoethanol of 5.5g ,-the 3 of 8.97g, the mono- acid anhydride-sylvite of 4,9,10- tetracarboxylic acids-, nitrogen imports, stirring, and 25 DEG C are anti-
It answers 2 hours, is warming up to 92 DEG C, react 2.5 hours.Heating stops, and stirring is to room temperature, with 31% hydrochloric acid, then by pH adjust to
Acidity, reaction product are precipitated, filtering, and 4L water washing to filtrate neutrality, 80 DEG C of dryings obtains the 3 of 8.54g, and 4,9,10- tetra-
Carboxylic acid-monoester anhydride-ω-hydroxyethyl amide (B), IR (KBr) measurement are as shown in Figure 3.
2) synthesis of 3,4,9,10- tetrabasic carboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl amide：Equipped with temperature
Degree is counted, blender, nitrogen ingress pipe, addition funnel, and 3,4,9, the 10- tetrabasic carboxylic acids-of 16.7g are added in the reaction flask of return pipe
Monoester anhydride-ω-hydroxyethyl amide, 7.5 grams of 3- diethyl amino propylamine, the DMF of 250g, stirring, nitrogen are imported, are heated to
It 80 DEG C, reacts 13 hours, is cooled to room temperature, pours into the distilled water of 1L, reactant is precipitated, and filters, and washing, 70 DEG C of dryings obtain
To the 3 of 18.7g, 4,9,10- tetrabasic carboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl amide (F).IR test knot
Fruit is as shown in Figure 4.
3) 3,4,9,10- tetrabasic carboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyl second of 5.47g is added in a kettle
Base amide, 90% potassium hydroxide of 0.72g, the propylene oxide of 21.0g under the conditions of argon gas, are heated to 70 DEG C, reaction 48 is small
When, remaining low boiling point reactant is sloughed, obtains the polymer D (dispersant A) of 8.6g, average molecular weight is about 800.
It is reacted by same feed ratio, reaction temperature is 80 DEG C, reacts 48 hours, sloughs remaining low boiling point reactant, obtain
To the polymer D (dispersant B) of 10.5g, average molecular weight is about 1000.
Embodiment 2 (application of graphene dispersion agent)
Add 1.0 grams of graphite in glass reaction container, (average molecular weight is about by 0.15 gram of graphene dispersion agent B
1000), 100 grams of distilled water, the zirconium pearl of 200 grams of 0.6-0.8mm, 500 watts of ultrasonic cleaner, ultrasound stripping in 16 hours
From.After glass, the separation of zirconium pearl, centrifuge separation, 5000rpm, 10 minutes.Take graphene upper clear liquid.Graphene concentration
1.8mg/mL。
The dispersion liquid is filtered with teflon membrane filter, and washed with 0.5% dilute hydrochloric acid it is colourless to filtrate, then with steaming
Distilled water is washed to filtrate neutrality, and graphene solid is collected, dry, obtains 0.16 gram of graphene.
Embodiment 3 (application of graphene dispersion agent)
The graphite of 1.0 grams of addition in glass reaction container, 0.20 gram of graphene dispersion agent A (average molecular weight is about 800),
100 grams of distilled water, the zirconium pearl of 200 grams of 0.6-0.8mm, 500 watts of ultrasonic cleaner, ultrasound removing in 16 hours.Glass
After, the separation of zirconium pearl, centrifuge separation, 5000rpm, 10 minutes.Take graphene upper clear liquid.Graphene concentration 2.0mg/mL.Stone
The thickness of black alkene concentration AFM measurement graphene, is less than or equal to 2.5nm (as shown in Figure 1).
Comparative example 1
The graphite of 1.0 grams of addition in glass reaction container, 100 grams of distilled water, the zirconium pearl of 200 grams of 0.6-0.8mm, 500
Watt ultrasonic cleaner, 16 hours ultrasound removing.After glass, the separation of zirconium pearl, centrifuge separation, 5000rpm.Take graphene
Upper clear liquid.Graphene concentration about 0.04mg/mL.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (8)
1. a kind of graphene dispersion agent, it is characterised in that：Chemical structural formula is as follows：
Wherein, R1, R2For the alkyl of C1 to C4；N=2 or 3 or 4 or 5 or 6；The alkyl of m=3~20, R3=hydrogen or C1 to C4, R
For hydrogen or the alkyl of C1 to C18.
2. a kind of preparation method of graphene dispersion agent as described in claim 1, it is characterised in that include the following steps：
1) 3, the synthesis of 4,9,10- tetrabasic carboxylic acids-monoester anhydride-ω-hydroxyethyl amide：3,4,9,10- tetracarboxylic acid dianhydrides exist
In potassium hydroxide aqueous solution, 85-95 DEG C of hydrolyzable, then adjusted pH to acidity with hydrochloric acid, obtain 3,4,9,10- tetramethyls
Acid-monoester anhydride-monopotassium salt；3,4,9,10- tetracarboxylic acids-monoester anhydride-monopotassium salt is in water phase and 2- ethylaminoethanol is in 85-95 DEG C
Lower reaction, then acid out obtain 3,4,9,10- tetracarboxylic acids-monoester anhydride-ω-hydroxyethyl amide (B)；
2) synthesis of 3,4,9,10- tetracarboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl amide：By step 1)
Gained 3,4,9,10- tetracarboxylic acids-monoester anhydride-ω-hydroxyethyl amide is in DMF solvent and excessive 3- diethylamino third
Amine reacts to obtain as follows 3,4,9,10- tetracarboxylic acid-N, N diethyl amino propyl amide-ω-hydroxyethyl amide
(C)；
3) by resulting 3,4,9,10- tetracarboxylic acid-N, N diethyl amino propyl amide-ω of step 2)-hydroxyethyl amide and
Excessive propylene oxide polymerize under potassium hydroxide catalysed, controls reaction condition, obtains such as graphene dispersion agent (D)；
3. preparation method as claimed in claim 2, which is characterized in that step 3) resulting graphene dispersion agent (D's) is averaged
Molecular weight is 700-1700.
4. a kind of application of graphene dispersion agent as described in claim 1 in graphene preparation, it is characterised in that including following
Step：Graphite, graphene dispersion agent, distilled water and zirconium pearl are added in container and mixed, carries out ultrasound under ultrasonic wave auxiliary
Removing；After removing, zirconium pearl is separated, is centrifugated, takes graphene upper clear liquid.
5. application as claimed in claim 4, which is characterized in that the graphite, graphene dispersion agent, distilled water and zirconium pearl matter
Amount is than being 1: 0.01-0.5: 20-200: 20-500.
6. application as described in claim 4 or 5, which is characterized in that the partial size of the zirconium pearl is 0.2-1.5mm.
7. application as claimed in claim 4, which is characterized in that every 1g graphene ultrasonic wave unit power is 20-200W, removing
Time is 10-100h.
8. application as claimed in claim 4, which is characterized in that the revolving speed of centrifuge separation is 1000-10000rpm.
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| CN201810822665.9A CN108862264B (en) | 2018-07-24 | 2018-07-24 | Graphene dispersing agent and preparation method and application thereof |
| PCT/CN2018/114685 WO2020019572A1 (en) | 2018-07-24 | 2018-11-09 | Graphene dispersant, preparation method therefor and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109851999A (en) * | 2018-12-27 | 2019-06-07 | 北京化工大学 | A kind of preparation method of carbon fibre composite |
| CN110183908A (en) * | 2019-03-19 | 2019-08-30 | 浙江省海洋开发研究院 | A kind of electrically conductive ink and preparation method thereof of containing graphene compound |
| CN113960120A (en) * | 2021-09-30 | 2022-01-21 | 中国科学院上海微***与信息技术研究所 | Sensor material based on perylene diimide, preparation method of sensor and application of sensor material |
| CN115777719A (en) * | 2022-10-08 | 2023-03-14 | 浙江省海洋开发研究院 | Perylene quaternary ammonium salt-graphene composite antibacterial agent and preparation method thereof |
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| CN109851999A (en) * | 2018-12-27 | 2019-06-07 | 北京化工大学 | A kind of preparation method of carbon fibre composite |
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| CN110183908A (en) * | 2019-03-19 | 2019-08-30 | 浙江省海洋开发研究院 | A kind of electrically conductive ink and preparation method thereof of containing graphene compound |
| CN110183908B (en) * | 2019-03-19 | 2022-03-22 | 浙江省海洋开发研究院 | Conductive ink containing graphene compound and preparation method thereof |
| CN113960120A (en) * | 2021-09-30 | 2022-01-21 | 中国科学院上海微***与信息技术研究所 | Sensor material based on perylene diimide, preparation method of sensor and application of sensor material |
| CN115777719A (en) * | 2022-10-08 | 2023-03-14 | 浙江省海洋开发研究院 | Perylene quaternary ammonium salt-graphene composite antibacterial agent and preparation method thereof |
| CN115777719B (en) * | 2022-10-08 | 2024-04-19 | 浙江省海洋开发研究院 | Perylene quaternary ammonium salt-graphene composite antibacterial agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108862264B (en) | 2021-08-17 |
| WO2020019572A1 (en) | 2020-01-30 |
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