CN106629670A - Method for dispersing carbon nano tubes by Gemini type dispersing agent - Google Patents
Method for dispersing carbon nano tubes by Gemini type dispersing agent Download PDFInfo
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Abstract
The invention discloses a method for dispersing carbon nano tubes by a Gemini type dispersing agent, relates to the field of dispersion of carbon nano tubes, and in particular relates to a method for dispersing carbon nano tubes by a novel dispersing agent (Gemini dispersing agent). According to the method, the surfaces of the carbon nano tubes are modified by virtue of a series of process flows, so that carbon nano tube aggregate is completely opened so as to form dispersion. The method comprises the following main implementation steps: (1) preparing a carbon nano tube dispersing agent 4,4-bis(myristyl) diphenylmethane bisulfonate solution; and (2) dispersing the carbon nano tubes. The method disclosed by the invention has the advantages of good effect, stable dispersion, easiness in operation, short process flow, short preparation cycle, little environmental pollution and the like.
Description
Technical field
The present invention relates to the field of dispersions of CNT, specially a kind of new carbon nano tube dispersion method.
Background technology
Since CNT (Carbon Nanotube, abbreviation CNT) self-discovery, its excellent mechanics, calorifics, electricity, light
Etc. performance increasingly causes all circles' extensive concern.The Young's modulus and modulus of shearing of CNT is all suitable with diamond, its axle
100GPa is up to the close 2TPa of Young's modulus, tensile strength, is 100 times of steel, be more than 20 times of high-strength carbon fiber, density
Only 1.35g/cm3Left and right, is 1/6, the 1/2 of aluminium, the 3/4 of magnesium of steel, meanwhile, CNT has good conduction, heat conduction
Performance, excellent self lubricity and biocompatibility.Therefore, CNT is considered as the matrix material such as ceramics, polymer, metal
The preferable hardening constituent of material.
Though CNT has many advantages, such as and be widely applied prospect, it is nano material, and draw ratio, surface area are very
Greatly, in order to reduce free energy, CNT tendency polymerization is agglomerating to reduce surface energy, and this is spontaneous trend behavior.Therefore in reality
In the application process of border, its reunion form often destroys excellent mechanics, the electrology characteristic that single-root carbon nano-tube is shown, from
And limit the application of CNT.The current predominantly organic tool method of process for dispersing of CNT, covalent bond modification method, non-covalent
Key modifies method.Such as " ball milling dispersing technology is on the scattered impact of CNT " (yellow people's richness. material Leader, 2013 (S2):The
35-38 page) dry type ball milling and wet ball-milling decentralized processing are carried out respectively to CNT in article, as a result show that CNT exists
Under the percussion of ball milling, CNT aggregate is opened to a certain extent.In a kind of " side for improving CNT dispersiveness
In the invention of method " (authorizing the A of publication No. CN 104861743), it discloses a kind of covalent bond modification method, and process for dispersing is first will
Cyclodextrin and silane coupler KH560 carry out reacting prepared KH560/ β-CD；Then CNT is acidified so that carbon is received
Substantial amounts of hydroxyl and carboxyl are introduced on mitron, obtains being acidified CNT；Finally KH560/ β-CD and acidifying CNT are entered
Row reaction is obtained cyclo-dextrin-modified CNT.
But, not only dispersion effect is poor for Mechanical Method, and mechanical external force can the unique structure of destroying carbon nanometer tube；Covalent bond
Though modification method to a certain extent can disperse CNT, covalent bond is inevitably introduced so as to change CNT
Structure, have impact on the performance of its special performance.During non-covalent bond modification method dispersing Nano carbon tubes, mainly with physical absorption, no
Produce covalent bond, thus will not destroying carbon nanometer tube structure, and modifying agent the later stage application in easily remove.Traditional is non-covalent
Key dispersant is mainly based on ionic, but its only one of which hydrophilic group and a lipophilic group, because this surfactant is dredged
There is balance in the centrifugation that charge repulsion and hydration cause between the association and ion head base between water chain so that it
In interface or molecule aggregate can not more close-packed arrays, so dispersibility is limited.Therefore, develop novel dispersant to change
The shortcoming of kind tradition non-covalent bond dispersant is to be badly in need of.
The content of the invention
The technical purpose of the present invention is primarily directed to the deficiency in current tradition dispersant CNT, and exploitation is a kind of
The method of the more preferable and more stable dispersing Nano carbon tubes of not destroying carbon nanometer tube structure newly, effect.The method is by new
Dispersant (Gemini dispersants) is modified the surface of CNT, improves its dissolubility, is then acted in ultrasonic vibration
Under make CNT aggregate scatter, form uniform and stable dispersion liquid.Dispersant used in method is 4,4- bis- (14
Alkyl) diphenyl-methane disulfonate.The method has good dispersion effect, stably dispersing, easy to operate, technological process is short, it is all to prepare
The advantages of phase is short, environmental pollution is little.
The present invention is achieved by the following technical solutions, a kind of method of Gemini type dispersant CNT,
Its step is：
(1) preparation of Carbon nano-tube dispersant solution；(2) decentralized processing of CNT.
It is specific as follows：
(1) preparation of Carbon nano-tube dispersant solution
4,4- bis- (myristyl) the diphenyl-methane disulfonate for weighing certain mass is added in solvent, and heating water bath is simultaneously
After insulation a period of time, stir to whole dissolvings, make 4,4- bis- (myristyl) diphenyl-methane disulfonate (double myristyls
Diphenyl-methane disulfonate) solution, bath temperature is 40～60 DEG C, and double myristyl diphenyl-methane disulfonate concentration are preferably
500～10000mg/L, is cooled to room temperature and obtains dispersant solution；
It is double that the above-mentioned double myristyl diphenyl-methane disulfonates for using are preferably 4,4- bis- (myristyl) diphenyl-methane
Sodium sulfonate, 4,4- bis- (myristyl) diphenyl-methane disulfonic acid potassium, solvent is preferably deionized water, ethanol and the two any ratio
The mixed liquor of example.
(2) decentralized processing of CNT
The CNT for weighing certain mass is added in the dispersant solution in step (1), and the concentration of CNT is excellent
Elect 100～2000mg/L as；Above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, carries out ultrasound, in ultrasound
Also intermittently adopt mechanical agitation simultaneously.It is preferred that ultrasonic time is 20～200min, being represented with T, mechanical agitation first carries out 0.1～
Rest 0.3～0.4T after 0.2T, then mechanical agitation is started again at, carry out being rested again after 0.1～0.2T 0.3～0.4T, with
This analogizes.It is preferred that mechanical agitation twice, is rested twice.
Above-mentioned CNT used can be SWCN, multi-walled carbon nano-tubes or two kinds of CNT different contents
Combination, and the purity of CNT is preferably not less than 99.0wt.%.
4,4- bis- (myristyl) diphenyl-methane disulfonic acid sodium, the knot of 4,4- bis- (myristyl) diphenyl-methane disulfonic acid potassium
Structure is as follows：
The principle of process for dispersing of the present invention is：CNT wall is mainly made up of carbon hexatomic ring, and each carbon is hexa-atomic
Nuclear carbon atom also has the p rails of a sky all based on sp2 hydridization in each carbon atom on the direction of tube wall
Road, on these p tracks highly delocalized big π keys are electronically formed, therefore in double myristyl diphenyl-methane disulfonates
Phenyl ring can be acted on by π-π stackings and form Non-covalent binding with CNT wall.In addition, double myristyl diphenyl-methanes are double
Hydrophobic end in sulfonate is alkyl chain, can this enhance double ten by hydrophobic binding effect absorption in carbon nano tube surface
The adhesion of tetraalkyl diphenyl-methane disulfonate and CNT.Double myristyl diphenyl-methane disulfonates have two parents
Water base i.e. ion head base, increasing, CNT is deliquescent simultaneously, makes carbon nano tube surface with electronegativity, is arranged using electrostatic
Effect is scolded to prevent CNT from reuniting again together, so as to obtain the stable carbon nano tube dispersion liquid that is uniformly dispersed, carbon nanometer
Pipe is completely dispersed.
Description of the drawings
Fig. 1 is that (CNT agglomerate particle average diameter is original carbon nanotubes aggregate low power SEM photograph
2694nm)；
Fig. 2 is original carbon nanotubes aggregate high power SEM photograph；
Fig. 3 is the homodisperse carbon nano-tube solution photo obtained in example 1；
Fig. 4 is through scattered CNT SEM photograph in example 1；
Fig. 5 is that (particle mean size of CNT is for the particle size distribution figure of CNT in carbon nano tube dispersion liquid in example 4
275.9nm)。
Specific embodiment
The present invention is further illustrated with reference to specific embodiment, it should be pointed out that following examples are served only for
The specific implementation method of the bright present invention, can not limit rights protection scope of the present invention.
Embodiment 1
(1) 4,4- bis- (myristyl) the diphenyl-methane disulfonic acid sodium for weighing 80mg is added in 40ml deionized waters, and 50
DEG C heating water bath is simultaneously incubated after 10min, is stirred to it and is all dissolved, and makes 4, the 4- bis- (myristyl) that concentration is 2000mg/L
Diphenyl-methane disulfonic acid sodium solution, is cooled to room temperature and obtains Carbon nano-tube dispersant solution.
(2) dispersant solution that 20mg multi-walled carbon nano-tubes (purity is 99.5wt.%) is added in step (1) is weighed
In, above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, then to its ultrasonic 60min, to it while ultrasonic
Carry out mechanical agitation, mechanical agitation carries out being rested after 10min 20min, then mechanical agitation carries out being rested again after 10min again
20min。
Embodiment 2
(1) 4,4- bis- (myristyl) the diphenyl-methane disulfonic acid sodium for weighing 20mg is added in 40ml deionized waters, and 40
DEG C heating water bath is simultaneously incubated after 10min, is stirred to it and is all dissolved, and makes 4, the 4- bis- (myristyl) that concentration is 500mg/L
Diphenyl-methane disulfonic acid sodium solution, is cooled to room temperature and obtains Carbon nano-tube dispersant solution.
(2) weigh 4mg SWCNs (purity is 99.5wt.%) to be added in the dispersant solution in step (1),
Above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, then to its ultrasonic 20min, it is entered while ultrasonic
Row mechanical agitation, mechanical agitation carries out being rested after 4min 6min, and then mechanical agitation carries out being rested again after 4min again 6min.
Embodiment 3
(1) 4,4- bis- (myristyl) the diphenyl-methane disulfonic acid sodium for weighing 400mg is added in 40ml deionized waters, and 60
DEG C heating water bath is simultaneously incubated after 20min, is stirred to it and is all dissolved, and makes (the tetradecanes of 4,4- bis- that concentration is 10000mg/L
Base) diphenyl-methane disulfonic acid sodium solution, it is cooled to room temperature and obtains Carbon nano-tube dispersant solution.
(2) dispersant solution that 80mg multi-walled carbon nano-tubes (purity is 99.5wt.%) is added in step (1) is weighed
In, above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, then to its ultrasonic 200min, while ultrasonic pair
It carries out mechanical agitation, and mechanical agitation carries out being rested after 20min 80min, and then mechanical agitation carries out stopping again after 20min again
Have a rest 80min.
Embodiment 4
(1) 4,4- bis- (myristyl) the diphenyl-methane disulfonic acid sodium for weighing 160mg is added in 40ml deionized waters, and 50
DEG C heating water bath is simultaneously incubated after 20min, is stirred to it and is all dissolved, and makes 4, the 4- bis- (myristyl) that concentration is 4000mg/L
Diphenyl-methane disulfonic acid sodium solution, is cooled to room temperature and obtains Carbon nano-tube dispersant solution.
(2) dispersant solution that 40mg multi-walled carbon nano-tubes (purity is 99.0wt.%) is added in step (1) is weighed
In, above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, then to its ultrasonic 100min, while ultrasonic pair
It carries out mechanical agitation, and mechanical agitation carries out being rested after 10min 30min, and then mechanical agitation carries out stopping again after 10min again
Have a rest 30min.
Embodiment 5
(1) 4,4- bis- (myristyl) the diphenyl-methane disulfonic acid potassium for weighing 80mg is added in 40ml deionized waters, and 50
DEG C heating water bath is simultaneously incubated after 10min, is stirred to it and is all dissolved, and makes 4, the 4- bis- (myristyl) that concentration is 2000mg/L
Diphenyl-methane disulfonic acid potassium solution, is cooled to room temperature and obtains Carbon nano-tube dispersant solution.
(2) dispersant solution that 20mg multi-walled carbon nano-tubes (purity is 99.0wt.%) is added in step (1) is weighed
In, above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, then to its ultrasonic 80min, to it while ultrasonic
Carry out mechanical agitation, mechanical agitation carries out being rested after 8min 25min, then mechanical agitation carries out being rested again after 8min again
25min。
Embodiment 6
(1) 4,4- bis- (myristyl) the diphenyl-methane disulfonic acid sodium for weighing 400mg is added in 40ml absolute ethyl alcohols, and 60
DEG C heating water bath is simultaneously incubated after 20min, is stirred to it and is all dissolved, and makes (the tetradecanes of 4,4- bis- that concentration is 10000mg/L
Base) diphenyl-methane disulfonic acid sodium solution, it is cooled to room temperature and obtains Carbon nano-tube dispersant solution.
(2) dispersant solution that 80mg multi-walled carbon nano-tubes (purity is 99.5wt.%) is added in step (1) is weighed
In, above-mentioned mixed liquor is placed in water-bath, bath temperature remains room temperature, then to its ultrasonic 200min, while ultrasonic pair
It carries out mechanical agitation, and mechanical agitation carries out being rested after 20min 80min, and then mechanical agitation carries out stopping again after 20min again
Have a rest 80min.
Claims (6)
1. a kind of method of Gemini type dispersant CNT, it is characterised in that comprise the following steps：
(1) preparation of Carbon nano-tube dispersant solution；(2) decentralized processing of CNT；
It is specific as follows：
(1) preparation of Carbon nano-tube dispersant solution
4,4- bis- (myristyl) the diphenyl-methane disulfonate for weighing certain mass is added in solvent, and heating water bath is simultaneously incubated
After a period of time, stir to whole dissolvings, make 4,4- bis- (myristyl) diphenyl-methane disulfonate (double myristyl hexichol
Methane disulfonate) solution, it is cooled to room temperature and obtains dispersant solution；
(2) decentralized processing of CNT
The CNT for weighing certain mass is added in the dispersant solution in step (1)；Above-mentioned mixed liquor is placed in into water-bath
In, bath temperature remains room temperature, carries out ultrasound, and mechanical agitation is also intermittently adopted while ultrasound.
2. according to a kind of method of the Gemini type dispersant CNT described in claim 1, it is characterised in that step
(1) bath temperature is 40～60 DEG C, and double myristyl diphenyl-methane disulfonate concentration are 500～10000mg/L.
3. according to a kind of method of the Gemini type dispersant CNT described in claim 1, it is characterised in that step
(1) the double myristyl diphenyl-methane disulfonates for using selected from for 4,4- bis- (myristyl) diphenyl-methane disulfonic acid sodium, 4,
4- bis- (myristyl) diphenyl-methane disulfonic acid potassium, solvent is the mixed liquor of deionized water, ethanol and the two arbitrary proportion.
4. according to a kind of method of the Gemini type dispersant CNT described in claim 1, it is characterised in that step
(2) concentration of the CNT in dispersant solution is 100～2000mg/L.
5. according to a kind of method of the Gemini type dispersant CNT described in claim 1, it is characterised in that step
(2) ultrasonic time is 20～200min, is represented with T, and mechanical agitation first carries out being rested after 0.1～0.2T 0.3～0.4T, Ran Houji
Tool stirring is started again at, and carries out being rested again after 0.1～0.2T 0.3～0.4T, by that analogy.
6. according to a kind of method of the Gemini type dispersant CNT described in claim 5, it is characterised in that machinery
Stirring twice, rests twice.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107988507A (en) * | 2017-12-10 | 2018-05-04 | 北京工业大学 | A kind of preparation method of high content of carbon nanotubes metal-base composites |
| CN109867776A (en) * | 2019-01-22 | 2019-06-11 | 江西铜业技术研究院有限公司 | A kind of Carbon nano-tube dispersant and its preparation method and application |
| CN109880090A (en) * | 2019-02-18 | 2019-06-14 | 华研(佛山)纳米材料有限公司 | The polyimides Heat Conduction Material of a kind of containing graphene and carbon nanotube, heat conducting film and preparation method thereof |
| CN110902670A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107988507A (en) * | 2017-12-10 | 2018-05-04 | 北京工业大学 | A kind of preparation method of high content of carbon nanotubes metal-base composites |
| CN110902670A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
| CN110902670B (en) * | 2018-09-14 | 2021-07-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube oriented film, preparation method and application thereof |
| CN109867776A (en) * | 2019-01-22 | 2019-06-11 | 江西铜业技术研究院有限公司 | A kind of Carbon nano-tube dispersant and its preparation method and application |
| CN109867776B (en) * | 2019-01-22 | 2021-08-31 | 江西铜业技术研究院有限公司 | Carbon nanotube dispersing agent and preparation method and application thereof |
| CN109880090A (en) * | 2019-02-18 | 2019-06-14 | 华研(佛山)纳米材料有限公司 | The polyimides Heat Conduction Material of a kind of containing graphene and carbon nanotube, heat conducting film and preparation method thereof |
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Application publication date: 20170510 |