CN102500255A - Carbon nano tube dispersing method - Google Patents

Carbon nano tube dispersing method Download PDF

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CN102500255A
CN102500255A CN2011103371264A CN201110337126A CN102500255A CN 102500255 A CN102500255 A CN 102500255A CN 2011103371264 A CN2011103371264 A CN 2011103371264A CN 201110337126 A CN201110337126 A CN 201110337126A CN 102500255 A CN102500255 A CN 102500255A
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carbon nano
nano tube
liquid
ionic
cnt
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靳健
李艳香
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The invention discloses a carbon nano tube dispersing method. Main steps of the method include a synthesizing polymerizable ionic liquid monomer; polymerizing the polymerizable ionic liquid into ionic liquid polymers via radical polymerization reaction, or preparing ionic liquid base polymers with imidazole ring functional groups; dissolving the ionic liquid polymers into a small quantity of organic solvent and preparing ionic liquid polymer solution with higher concentration; mixing the ionic liquid base polymers adopted as dispersing agent with a carbon nano tube, mechanically grinding the mixture, leading poly ionic liquid to uniformly coat on the surface of the carbon nano tube, and obtaining gel; and adding a large quantity of organic solvent in the gel, ultrasonically dispersing the mixture, and then centrifugally separating the mixture so as to obtain carbon nano tube dispersing liquid. The carbon nano tube dispersing method is fine in stability and uniform in dispersing, and the dispersing liquid can be stored for a long time.

Description

A kind of carbon nano tube dispersion method
Technical field
The present invention relates to a kind of carbon nano tube dispersion method, in particular, relate to the carbon nano tube dispersion method of a kind of ionic-liquid-base polymer as dispersant.
Background technology
CNT has caused the very big interest of academia and industrial circle since finding.CNT has high-specific surface area and high draw ratio, and good mechanics, electricity and thermal property are considered to the desirable filler of polymeric material, can strengthen polymer, improve conducting polymer heat conductivility etc.Realize above-mentioned target, the dispersion of CNT is very important link.Interaction and mutual winding the strong between CNT make CNT be difficult to evenly disperse.CNT adopts the method for ultrasonic dispersion to disperse usually, and the dispersant of employing mainly is a surfactant, like neopelex.But the less stable of this type dispersant, the CNT deposited phenomenon can take place in long preservation.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the shortcoming of prior art, but a kind of good stability is provided, the process for dispersing of the long preservation that is uniformly dispersed CNT.
In order to solve above technical problem; The present invention provides a kind of carbon nano tube dispersion method; The employing ionic-liquid-base polymer is a dispersant; CNT is mixed by mass ratio 1:1-1:100 with ionic-liquid-base polymer, after grinding, add the ultrasonic dispersion of organic solvent, centrifugation, obtain uniform CNT dispersion liquid.
The technical scheme that the present invention further limits is: comprise step:
I, synthetic polymerisable ionic liquid monomer;
II, through Raolical polymerizable polymerisable ionic liquid monomer polymerization is become to have the ionic-liquid-base polymer of imidazole group;
III, ionic-liquid-base polymer is dissolved in processes ionic-liquid-base polymer solution in the organic solvent, and mix with CNT as dispersant with this, mechanical lapping evenly is coated on carbon nano tube surface with ionic-liquid-base polymer solution and is gelling material;
IV, in gelling material, add organic solvent, and the centrifugation of ultrasonic dispersion back, uniform CNT dispersion liquid obtained.
Further: the general formula of polymerisable ionic liquid monomer described in the step I is A +B -Type comprises at least:
Figure 886944DEST_PATH_IMAGE001
；
Wherein, A +For having the cation of imidazole group, wherein R 1-R 4Be alkyl independently separately; B -Be at least Cl, Br, I, tetrafluoro boric acid (BF 4), hexafluorophosphoric acid (PF 6), two fluoroform sulfimide (Tf 2N), TFMS (CF 3SO 3) or the anion of dicyandiamide (dca).
Further: ionic-liquid-base polymer comprises at least described in the step II:
Figure 2011103371264100002DEST_PATH_IMAGE002
；
Wherein, A +For having the cation of imidazole group, wherein R 1-R 5Be alkyl independently separately, R 6Be polymer; B -Be at least Cl, Br, I, tetrafluoro boric acid (BF 4), hexafluorophosphoric acid (PF 6), two fluoroform sulfimide (Tf 2N), TFMS (CF 3SO 3) or the anion of dicyandiamide (dca).
Further: CNT described in the step III is the single armed CNT, and the concentration of CNT is less than 0.02mg/ml.
Further: the time of mechanical lapping was between 10～60 minutes in the step III.
Further: the time of ultrasonic dispersion was between 2～8 hours in the step IV.
Further: organic solvent is the N-methyl pyrrolidone described in step III and the step IV; N, dinethylformamide; N, the N-dimethylacetylamide; Carrene; Chloroform or acetone.
The invention has the beneficial effects as follows: carbon nano tube dispersion method of the present invention adopts ionic-liquid-base polymer as dispersant; On the one hand, ionic liquid interacts through cation-л and л-л interacts and the electron production strong interaction of carbon nano tube surface, on the other hand; Polymer plays and is similar to influence of surfactant; Both synergies make ion liquid polymer evenly be coated on carbon nano tube surface, thereby realize the dispersion of even carbon nanotube; Good stability, but long preservation; Because dispersion process is not introduced chemical compositions such as other surfactants, the ionic-liquid-base polymer coated carbon nano-tube composite material that obtains can be used for fields such as nano-sensor, energy storage device, catalysis, separation.
Description of drawings
Fig. 1 is a carbon nano tube dispersion method flow chart of the present invention;
Fig. 2 is the scatter diagram of transmission electron microscope observation to CNT;
Fig. 3 evenly coats one layer of polymeric for transmission electron microscope observation to carbon nano tube surface.
The specific embodiment
Embodiment 1
A kind of carbon nano tube dispersion method that present embodiment provides, flow chart is as shown in Figure 1, comprises following steps:
I, synthetic polymerisable ionic liquid monomer;
II, through Raolical polymerizable polymerisable ionic liquid monomer polymerization is become to have the ionic-liquid-base polymer of imidazole group;
III, title 20mg ionic-liquid-base polymer, gather (1-(2-(methylacryoyloxyethyl)-3-butyl tetrafluoroborate) adds 1mL N, dinethylformamide, and stirring is dissolved.Get the above-mentioned ionic-liquid-base polymer solution of 50 μ l and join in the agate mortar, and add 1mg single armed CNT, hand-ground 10min obtains the black gelling material.
IV, the black jelly is transferred in the blue lid bottle, use N, dinethylformamide is rinsed mortar well, and flushing liquor together joins in the blue lid bottle, adds N then, and dinethylformamide is to cumulative volume 200ml.Ultrasonic 2-8 hour, preferred 3 hours, centrifugal, keep supernatant, promptly obtain the CNT dispersion liquid.
This dispersion liquid stable homogeneous is placed and was not still had deposition in 6 months.This CNT dispersant liquid drop is after drying on the copper mesh, and transmission electron microscope observation well disperses to CNT, and carbon nano tube surface evenly coats one layer of polymeric.
This CNT dispersant liquid drop is after drying on the copper mesh, and transmission electron microscope observation is to the scatter diagram of CNT, and is as shown in Figure 1, and carbon nano tube surface evenly coats one layer of polymeric, and is as shown in Figure 2.
Embodiment 2
A kind of carbon nano tube dispersion method that present embodiment provides, flow chart is as shown in Figure 1, comprises following steps:
Step I and step II such as embodiment 1 are said.
III is claimed 20mg ionic-liquid-base polymer, gathers (1-vinyl-3-ethyl imidazol(e) trifluoromethane sulfonic acid amine salt), adds 1ml N, and the N-dimethylacetylamide stirs, dissolving.Get the above-mentioned ionic-liquid-base polymer solution of 100 μ l and join in the agate mortar, and add 1mg single armed CNT, hand-ground 30min obtains the black gelling material.
IV is transferred to the black jelly in the blue lid bottle, uses N, and the N-dimethylacetylamide is rinsed mortar well, and flushing liquor together joins in the blue lid bottle, adds N then, and the N-dimethylacetylamide is to cumulative volume 500ml.Ultrasonic 2-8 hour, preferred 2 hours, centrifugal, keep supernatant, promptly obtain the CNT dispersion liquid.
Embodiment 3
A kind of carbon nano tube dispersion method that present embodiment provides, flow chart is as shown in Figure 1, comprises following steps:
Step I and step II such as embodiment 1 are said.
III is claimed 20mg ionic-liquid-base polymer, gathers (1-(4-ethylene benzyl)-3-butyl imidazole hexafluoro borate), adds 1ml N, and dinethylformamide stirs, dissolving.Get the above-mentioned ionic-liquid-base polymer solution of 200 μ l and join in the agate mortar, and add 1mg single armed CNT, hand-ground 50min obtains the black gelling material.
IV is transferred to the black jelly in the blue lid bottle, uses N, and dinethylformamide is rinsed mortar well, and flushing liquor together joins in the blue lid bottle, adds N then, and dinethylformamide is to cumulative volume 300ml.Ultrasonic 2-8 hour, preferred 6 hours, centrifugal, keep supernatant, promptly obtain the CNT dispersion liquid.
Embodiment 4
A kind of carbon nano tube dispersion method that present embodiment provides, flow chart is as shown in Figure 1, comprises following steps:
Step I and step II such as embodiment 1 are said.
III is claimed 20mg ionic-liquid-base polymer, gathers (1-vinyl-3-methylimidazole bromine salt), adds the 1mlN-methyl pyrrolidone, stirs dissolving.Get above-mentioned ionic-liquid-base polymer solution and join in the agate mortar, and add 1mg single armed CNT, hand-ground 30min obtains the black gelling material.
IV is transferred to the black jelly in the blue lid bottle, with the N-methyl pyrrolidone mortar is rinsed well, and flushing liquor together joins in the blue lid bottle, adds the N-methyl pyrrolidone then to cumulative volume 300ml.Ultrasonic 2-8 hour, preferred 8 hours, centrifugal, keep supernatant, promptly obtain the CNT dispersion liquid.
Embodiment 5
A kind of carbon nano tube dispersion method that present embodiment provides, flow chart is as shown in Figure 1, comprises following steps:
Step I and step II such as embodiment 1 are said.
III is claimed 20mg ionic-liquid-base polymer, gathers (1-(the two fluoroform sulfimide salt of 2-(methylacryoyloxyethyl)-3-hexyl imidazoles), adding 1ml carrene, stirring, dissolving.Get the above-mentioned ionic-liquid-base polymer solution of 100 μ l and join in the agate mortar, and add 1mg single armed CNT, hand-ground 1h obtains the black gelling material.
IV is transferred to the black jelly in the blue lid bottle, with carrene mortar is rinsed well, and flushing liquor together joins in the blue lid bottle, adds methylene chloride then to cumulative volume 400ml.Ultrasonic 2-8 hour, preferred 5 hours, centrifugal, keep supernatant, promptly obtain the CNT dispersion liquid.
Except that the foregoing description, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.

Claims (8)

1. carbon nano tube dispersion method; It is characterized in that: the employing ionic-liquid-base polymer is a dispersant; CNT is mixed by mass ratio 1:1-1:100 with ionic-liquid-base polymer, after grinding, add the ultrasonic dispersion of organic solvent, centrifugation, obtain uniform CNT dispersion liquid.
2. a kind of carbon nano tube dispersion method according to claim 1 is characterized in that comprising step:
I, synthetic polymerisable ionic liquid monomer;
II, through Raolical polymerizable polymerisable ionic liquid monomer polymerization is become to have the ionic-liquid-base polymer of imidazole group;
III, ionic-liquid-base polymer is dissolved in processes ionic-liquid-base polymer solution in the organic solvent, and mix with CNT as dispersant with this, mechanical lapping evenly is coated on carbon nano tube surface with ionic-liquid-base polymer solution and is gelling material;
IV, in gelling material, add organic solvent, and the centrifugation of ultrasonic dispersion back, uniform CNT dispersion liquid obtained.
3. a kind of carbon nano tube dispersion method according to claim 2 is characterized in that: the general formula of polymerisable ionic liquid monomer described in the step I is A +B -Type comprises at least:
Figure 561775DEST_PATH_IMAGE001
；
Wherein, A +For having the cation of imidazole group, wherein R 1-R 4Be alkyl independently separately; B -Be at least Cl, Br, I, tetrafluoro boric acid BF 4, hexafluorophosphoric acid PF 6, two fluoroform sulfimide Tf 2N, TFMS CF 3SO 3Or the anion of dicyandiamide dca.
4. a kind of carbon nano tube dispersion method according to claim 2 is characterized in that: ionic-liquid-base polymer comprises at least described in the step II:
Figure 2011103371264100001DEST_PATH_IMAGE002
；
Wherein, A +For having the cation of imidazole group, wherein R 1-R 5Be alkyl independently separately, R 6Be polymer; B -Be at least Cl, Br, I, tetrafluoro boric acid BF 4, hexafluorophosphoric acid PF 6, two fluoroform sulfimide Tf 2N, TFMS CF 3SO 3Or the anion of dicyandiamide dca.
5. a kind of carbon nano tube dispersion method according to claim 2 is characterized in that: CNT described in the step III is the single armed CNT, and the concentration of CNT is less than 0.02mg/ml.
6. a kind of carbon nano tube dispersion method according to claim 2 is characterized in that: the time of mechanical lapping was between 10～60 minutes in the step III.
7. a kind of carbon nano tube dispersion method according to claim 2 is characterized in that: the time of ultrasonic dispersion was between 2～8 hours in the step IV.
8. a kind of carbon nano tube dispersion method according to claim 1 is characterized in that: organic solvent is the N-methyl pyrrolidone described in step III and the step IV; N, dinethylformamide; N, the N-dimethylacetylamide; Carrene; Chloroform or acetone.
CN2011103371264A 2011-10-31 2011-10-31 Carbon nano tube dispersing method Pending CN102500255A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102877367A (en) * 2012-10-26 2013-01-16 中国科学院苏州纳米技术与纳米仿生研究所 Carbon nanotube/short-fiber composited nano-carbon paper and continuous preparation method thereof
CN103146231A (en) * 2013-03-15 2013-06-12 北京化工大学 Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid
CN103149229A (en) * 2013-03-04 2013-06-12 四川汉龙新材料有限公司 Method for detecting material compositions and contents thereof of welding material
CN104923095A (en) * 2015-06-11 2015-09-23 长沙理工大学 Physical dispersing method for carbon nano-tube
CN117467226A (en) * 2023-12-28 2024-01-30 上海拜安传感技术有限公司 Composition, sensing film, sensor, preparation method and application

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CN101037198A (en) * 2007-02-09 2007-09-19 浙江大学 Carbon nano tube with high water-solubility and preparation method thereof
CN102180458A (en) * 2011-03-25 2011-09-14 深圳市贝特瑞纳米科技有限公司 Nano-carbon material dispersion liquid and preparation method and equipment thereof

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CN101037198A (en) * 2007-02-09 2007-09-19 浙江大学 Carbon nano tube with high water-solubility and preparation method thereof
CN102180458A (en) * 2011-03-25 2011-09-14 深圳市贝特瑞纳米科技有限公司 Nano-carbon material dispersion liquid and preparation method and equipment thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102877367A (en) * 2012-10-26 2013-01-16 中国科学院苏州纳米技术与纳米仿生研究所 Carbon nanotube/short-fiber composited nano-carbon paper and continuous preparation method thereof
CN103149229A (en) * 2013-03-04 2013-06-12 四川汉龙新材料有限公司 Method for detecting material compositions and contents thereof of welding material
CN103146231A (en) * 2013-03-15 2013-06-12 北京化工大学 Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid
CN103146231B (en) * 2013-03-15 2014-12-03 北京化工大学 Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid
CN104923095A (en) * 2015-06-11 2015-09-23 长沙理工大学 Physical dispersing method for carbon nano-tube
CN117467226A (en) * 2023-12-28 2024-01-30 上海拜安传感技术有限公司 Composition, sensing film, sensor, preparation method and application
CN117467226B (en) * 2023-12-28 2024-03-19 上海拜安传感技术有限公司 Composition, sensing film, sensor, preparation method and application

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Application publication date: 20120620