CN106517152A - Method for uniform dispersion of single-walled carbon nanotubes in water solvent - Google Patents
Method for uniform dispersion of single-walled carbon nanotubes in water solvent Download PDFInfo
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- CN106517152A CN106517152A CN201610946073.9A CN201610946073A CN106517152A CN 106517152 A CN106517152 A CN 106517152A CN 201610946073 A CN201610946073 A CN 201610946073A CN 106517152 A CN106517152 A CN 106517152A
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- C01B2202/00—Structure or properties of carbon nanotubes
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Abstract
The invention discloses a method for uniform dispersion of single-walled carbon nanotubes in a water solvent. The method includes the steps: firstly under the protection of inert atmosphere, employing a tetrahydrofuran solution of naphthylsodium to make the surfaces of carbon nanotubes positively charged, and allowing carbon nanotube bundles to spontaneously disperse in a dimethyl sulfoxide solvent through the repulsive force between the charged carbon nanotubes; then adding polyvinylpyrrolidone to protect carbon nanotubes losing charges in air atmosphere and make the carbon nanotubes maintain a disperse state; and then converting a dispersion solvent of the polyvinylpyrrolidone coated single-walled carbon nanotubes from dimethyl sulfoxide into water by dialysis. The method realizes solubility of single-walled carbon nanotubes, and at the same time maintains the structural integrity and original properties of the single-walled carbon nanotubes. Under the premise of no need of ultrasound and surface functionalization, the method realizes uniform dispersion of the single-walled carbon nanotubes in the water solvent. The carbon nanotubes uniformly and stably dispersed in a water phase are of important significance for promoting the application of carbon nanotubes in biomedicine, chemistry, physics, composite materials and other fields.
Description
Technical field
The invention belongs to CNT field of dispersions, the more particularly to SWCN homodisperse side in aqueous solvent
Method.
Background technology
CNT can regard the hollow seamless structure curled into by Graphene as, and the pipe shaft of CNT is by six
Side shape graphite carbon ring construction unit composition.It is excellent that the unique structure of CNT, particularly SWCN creates which
The property of the aspects such as physics, chemistry, electricity, optics, therefore since rising for birth just causes the great interest of scientific circles and wide
General concern.However, the SWCN for preparing is generally easy to due to Van der Waals force strong between its big draw ratio and carbon pipe
Form larger tube bank, it is difficult to disperse, weaken the excellent properties of SWCN, greatly constrain its subsequent applications.
In order to obtain homodisperse SWCN, researcher is continuously attempted to, and has developed various carbon modifieds
Nanotube mainly includes in the method for improving dispersibility in a solvent：Covalent functionalization and non-covalent functionalization.Covalent function
Change is to make functional group in CNT grafting by the method for covalent modification, therefore, it is possible to be dissolved in various organic and inorganic solvent
In.But the complete structure of CNT itself is destroyed while covalent functionalization, many SP2 is introduced in CNT miscellaneous
Change defect, destroy optics, the electric property of SWCN essence, reduce the mechanical property of CNT.It is non-covalent
Key functionalization refers to that SWCN is passed through with surfactant, polymer, bioactive molecule or the molecule containing big π keys
π-π interact or Van der Waals force is combined, and improve the dispersive property of CNT.But in dispersion process, generally using strength
Ultrasonic wave realize cladding and the dispersion of SWCN.And strong ultrasonic wave has not only blocked SWCN, and
And a lot of defects are brought in itself to carbon pipe.Therefore, the performance of scattered CNT is had a greatly reduced quality, and greatly constrains which excellent
The performance of different in nature energy and practical application.In view of the using value of SWCN, need the method for a milder to divide
Throwaway wall carbon nano tube.
The content of the invention
In order to overcome above-mentioned deficiency, the invention provides a kind of method for disperseing SWCN in a mild condition,
To overcome the shortcoming of functionalization destroying carbon nanometer tube structure.The present invention combines powered SWCN in aprotic solvent
Spontaneous dissolving and polymer cladding and osmotic technique to SWCN, realize the dispersed of CNT.Keep away
Ultrasound or destruction of the covalent functionalization to complete carbon nano tube structure are exempted from so that SWCN Surface coating water solubility
Macromolecular compound, so as to reach dispersion of the SWCN in water.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of SWCN homodisperse method in aqueous solvent, including：
SWCN is surface-treated using sodium-naphthalene solution, obtains powered SWCN；
Make the powered SWCN self-dispersing carry out coating to which in polar solvent, using covering, dialysis,
Obtain final product the SWCN aqueous solution.
Due to most inorganic agent, covalent functionalization can be produced to carbon pipe, so as to the original performance of destroying carbon nanometer tube.
Therefore, the present invention carries out Large-scale Screening to existing inorganic agent, finds：Using sodium-naphthalin treatment solution to CNT at
During reason, due to the chemical inertness of CNT itself, there is no chemical reaction and polarization base in its tube wall with sodium-naphthalin treatment solution
Group.And CNT can only be made positively charged, generate [Na (THF)]nNT (sodium-tetrahydrofuran-CNT) colloidal sol, these bands
Repulsive force between electrical carbon nanotube is the basis that CNT thermoplastic polymer forms colloidal sol.The CNT of this thermoplastic polymer
Concentration in dimethyl sulfoxide (DMSO) can reach 0.4mg/g.
On the other hand, the stability based on the carbon pipe colloidal sol for preparing, the present invention have been selected the PVP of non-electrolyte to coat point
Scattered CNT, the aggregation without causing carbon pipe, it is to avoid carbon nanotube sol occurs coagulation under electrolyte effect.Together
When, as PVP had both been dissolved in water, organic solvent dimethyl sulfoxide (DMSO) is dissolved in again, therefore is adapted to dialysis, it is stable in not destroying carbon nanometer tube
Property on the premise of, the solvent of CNT that PVP is coated is switched to water phase from organic phase.
Preferably, in the sodium-naphthalene solution and SWCN, sodium, naphthalene, the mass ratio of SWCN are 0.07
～00.9：0.384～0.4：0.2～0.24.When the mass ratio of naphthalene, SWCN is more than 2, excessive anion freedom
Base is easily assembled with positively charged CNT, destruction Na (THF)]nNT (sodium-tetrahydrofuran-CNT) colloidal sols are stablized
Property；When the mass ratio of naphthalene, SWCN is less than 1.6, the repulsive force between CNT is less, molten in polar solvent
Solution property declines.
Preferably, the powered SWCN and the mass ratio of covering are 1～10：10～1.When single wall carbon is received
When the ratio of mitron and covering is more than 10, the stability of CNT declines, easily assembles, and dialysis effect is poor；When single wall carbon is received
When the ratio of mitron and covering is less than 1/10, continue to increase covering ratio, to CNT, in water, dissolubility is lifted not
Greatly.
Preferably, the polar solvent is dimethyl sulfoxide (DMSO), chloroform, dichloromethane or aromatic solvent.
Preferably, the covering is not only to be dissolved in organic solvent but also is dissolved in the polymer overmold agent of water.
It is furthermore preferred that the polymer overmold agent is polyvinylpyrrolidone PVP, poly- (propionyl ethylenimine -co- Asia
Ethyl ethamine) PPEI-EI or polyvinylsulfonic acid salt.
Preferably, without the need for ultrasonically treated in each step of methods described.
Preferably, the dialysis is processed makes the solvent of SWCN change into water by organic solvent.
Present invention also offers the homodisperse method of one kind preferably SWCN, comprises the steps：
1) in the glove box of nitrogen protection, 0.384g naphthalenes and 0.07g sodium are dissolved in into 100 milliliters of tetrahydrofurans, are acutely stirred
Mixing makes all solids all dissolve.
2) about 200mg SWCNs (HiPco, NanoIntegris, USA) are added into above-mentioned naphthyl sodium solution, is stirred
After mixing 12 hours, filter, and rinsed to efflux as colourless with tetrahydrofuran.
3), after being vacuum dried, the SWCN after 20mg is processed is placed in 50mL dimethyl sulfoxide (DMSO)s, stirring and dissolving.
4) by 50mg polyvinylpyrrolidone (molecular weight：90, in 000) adding the dimethyl sulphoxide solution of carbon pipe, stirring
To being completely dissolved.
5) solution of carbon pipe is taken out from glove box, is exposed in air, imported pellicle bag, be placed in and fill distilled water
Beaker in dialysis, and repeatedly change distilled water.The uniform SWCN aqueous solution is obtained after the completion of dialysis.
First under inert atmosphere protection, carbon nano tube surface all positively chargeds are made using the tetrahydrofuran solution of sodium naphthalene
Lotus, makes carbon nano-tube bundle thermoplastic polymer in dimethyl sulfoxide solvent with the repulsive force between electrical carbon pipe.It is subsequently adding polyethylene
Pyrrolidones protection loses the carbon pipe of electric charge in air atmosphere and is allowed to keep dispersity.The method of dialysis is recycled to make to gather
The dispersion solvent of the SWCN of vinylpyrrolidone cladding is converted to water by dimethyl sulfoxide (DMSO).
Present invention also offers the SWCN aqueous solution prepared by the above-mentioned method of any one.The carbon nanometer of the present invention
The concentration of pipe, substantially can with retainer belt electrical carbon nanotube dimethyl sulfoxide concentration, both 0.4mg/g, more than common CNT
Solubility.Certainly, as the dispersion of CNT is built upon on the basis with electrical carbon pipe of thermoplastic polymer, therefore,
It is dispersed more preferable, just as the characterization result of AFM (Fig. 3) and transmission electron microscope (Fig. 4) shows.
Present invention also offers the above-mentioned SWCN aqueous solution is being prepared in field emission display, nanoelectronic
Application in device, super-strength composite.
Beneficial effects of the present invention
(1) principle of the invention be based primarily upon powered SWCN can thermoplastic polymer in organic solvent, and
Using being not only dissolved in organic solvent but also be dissolved in the non ionic polymer compound carbon coated pipe of water, and with reference to the method for dialysis, reach
SWCN in a solvent dispersed and the structure of CNT and performance are substantially unaffected.
(2) present invention, avoiding the ultrasound and covalent functionalization damaged to carbon tubular construction so that complete carbon nanometer
The pipe surface grafting group of functionalization, realizes the solubility of SWCN, while also maintaining single walled carbon nanotubes sheet
The structural intergrity of body and the characteristic of itself.The present invention is simple, it is easy to carry out large-scale industrial production.
(3) preparation method of the present invention is simple, dissolution rate is high, practical, it is easy to promote.
Description of the drawings
Fig. 1 is the schematic flow sheet of the present invention.
Fig. 2 is the photo of carbon nano-tube aqueous solutions and microphotograph obtained in the embodiment of the present invention 1.
Fig. 3 is the scattered atomic force microscope images of CNT water obtained by the embodiment of the present invention 1.
Fig. 4 is the scattered transmission electron microscope picture of CNT water obtained by the embodiment of the present invention 1, indicates single wall carbon and receives
The polymolecularity of mitron.
Fig. 5 is the ultraviolet-visible-infrared absorpting light spectra of the carbon nano-tube aqueous solutions obtained by inventive embodiments 1, shows
The SWCN for obtaining has very high dispersiveness.
Specific embodiment
By the following examples feature of present invention and other correlated characteristics are described in further detail, in order to the same industry
The understanding of technical staff：
Embodiment one
1) in the glove box of nitrogen protection, 0.384g naphthalenes and 0.07g sodium are dissolved in into 100 milliliters of tetrahydrofurans, are acutely stirred
Mixing makes all solids all dissolve.
2) about 200mg SWCNs (HiPco, NanoIntegris, USA) are added into above-mentioned naphthyl sodium solution, is stirred
After mixing 12 hours, filter, and rinsed to efflux as colourless with tetrahydrofuran.
3) after being vacuum dried, the SWCN after 2.5mg is processed is placed in 50mL dimethyl sulfoxide (DMSO)s, is stirred molten
Solution.
4) by 50mg polyvinylpyrrolidone (molecular weight：90, in 000) adding the dimethyl sulphoxide solution of carbon pipe, stirring
To being completely dissolved.
5) solution of carbon pipe is taken out from glove box, is exposed in air, imported pellicle bag, be placed in and fill distilled water
Beaker in dialysis, and repeatedly change distilled water.The uniform SWCN aqueous solution is obtained after the completion of dialysis, solubility is
0.40mg/g。
Embodiment two
With embodiment 1, by step 4) in the quality adjustment of polyvinylpyrrolidone be 0.5mg, other reaction conditions are constant,
The homodisperse SWCN aqueous solution is obtained, solubility is 0.39mg/g.
Embodiment three
With embodiment 1, by step 4) quality adjustment of polyvinylpyrrolidone is 1000mg, other reaction conditions are constant,
The homodisperse SWCN aqueous solution is obtained, solubility is 0.41mg/g.
Example IV
With embodiment 1, by step 3) quality adjustment of SWCN is 20.0mg, other reaction conditions are constant,
The aqueous solution obtains the homodisperse SWCN aqueous solution, and solubility is 0.42mg/g.
Embodiment five
With embodiment 1, by step 3) quality adjustment of SWCN is 10.0mg, other reaction conditions are constant,
The aqueous solution obtains the SWCN of coagulation, and solubility is 0.40mg/g.
Embodiment six
With embodiment 1, save step 4), other reaction conditions are constant, obtain the SWCN of coagulation.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, this is not limited to
Bright, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, which is still
Technical scheme described in previous embodiment can be modified, or equivalent is carried out to which part.It is all at this
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc. should be included in protection scope of the present invention
Within.Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to the scope of the present invention
Restriction, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
The various modifications made by creative work is paid or deformation are still within protection scope of the present invention.
Claims (10)
1. a kind of SWCN homodisperse method in aqueous solvent, it is characterised in that include：
SWCN is surface-treated using sodium-naphthalene solution, obtains powered SWCN；
Make the powered SWCN self-dispersing carry out coating to which in polar solvent, using covering, dialysis, obtain final product
The SWCN aqueous solution.
2. the method for claim 1, it is characterised in that in the sodium-naphthalene solution and SWCN, sodium, naphthalene, list
The mass ratio of wall carbon nano tube is 0.07～00.9：0.384～0.4：0.2～0.24.
3. the method for claim 1, it is characterised in that the mass ratio of the powered SWCN and covering
For 1～10：10～1.
4. the method for claim 1, it is characterised in that the polar solvent is dimethyl sulfoxide (DMSO), chloroform, dichloromethane
Or aromatic solvent.
5. the method for claim 1, it is characterised in that the covering is not only to be dissolved in organic solvent but also is dissolved in the poly- of water
Compound covering.
6. method as claimed in claim 5, it is characterised in that the polymer overmold agent is polyvinylpyrrolidone PVP, poly-
(propionyl ethylenimine -co- ethylidene ethamine) PPEI-EI or polyvinylsulfonic acid salt.
7. the method for claim 1, it is characterised in that without the need for ultrasonically treated in each step of methods described.
8. the method for claim 1, it is characterised in that the dialysis is processed makes the solvent of SWCN by organic
Solvent conversion Cheng Shui.
9. the SWCN aqueous solution that prepared by the method described in any one of claim 1-8.
10. the SWCN aqueous solution described in claim 9 prepare field emission display, nano electron device,
Application in super-strength composite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592670A (en) * | 2018-12-20 | 2019-04-09 | 湖北工程学院 | The dispersing method of single-walled carbon nanotube |
| CN109603697A (en) * | 2018-12-24 | 2019-04-12 | 施柏山 | A kind of nano-sized carbon mixes aeroge and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2494961C2 (en) * | 2011-03-04 | 2013-10-10 | Общество с ограниченной ответственностью "НаноТехЦентр" | Dispersion of carbon nanotubes |
| CN103400991A (en) * | 2013-08-13 | 2013-11-20 | 天奈(镇江)材料科技有限公司 | Water-based carbon nanotube slurry and preparation method thereof |
| CN104445151A (en) * | 2014-12-02 | 2015-03-25 | 张满锦 | Method for preparing water-soluble multi-walled carbon nanotube |
-
2016
- 2016-11-02 CN CN201610946073.9A patent/CN106517152B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2494961C2 (en) * | 2011-03-04 | 2013-10-10 | Общество с ограниченной ответственностью "НаноТехЦентр" | Dispersion of carbon nanotubes |
| CN103400991A (en) * | 2013-08-13 | 2013-11-20 | 天奈(镇江)材料科技有限公司 | Water-based carbon nanotube slurry and preparation method thereof |
| CN104445151A (en) * | 2014-12-02 | 2015-03-25 | 张满锦 | Method for preparing water-soluble multi-walled carbon nanotube |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592670A (en) * | 2018-12-20 | 2019-04-09 | 湖北工程学院 | The dispersing method of single-walled carbon nanotube |
| CN109603697A (en) * | 2018-12-24 | 2019-04-12 | 施柏山 | A kind of nano-sized carbon mixes aeroge and its preparation method and application |
| CN109603697B (en) * | 2018-12-24 | 2022-02-15 | 施柏山 | Nano carbon hybrid aerogel and preparation method and application thereof |
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