CN109081329A - A kind of separation method and system of carbon nanotube and polymer - Google Patents
A kind of separation method and system of carbon nanotube and polymer Download PDFInfo
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- CN109081329A CN109081329A CN201811149190.8A CN201811149190A CN109081329A CN 109081329 A CN109081329 A CN 109081329A CN 201811149190 A CN201811149190 A CN 201811149190A CN 109081329 A CN109081329 A CN 109081329A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
Abstract
The invention discloses the separation methods and system of a kind of carbon nanotube and polymer.The described method includes: providing carbon nano tube dispersion liquid, the carbon nano tube dispersion liquid includes carbon nanotube, polymer and organic solvent as Carbon nano-tube dispersant, wherein polymer and carbon nanotube by physical action in conjunction with；The regional area of substrate is at least immersed into aqueous phase system, and forms airwater mist cooling parting line in the intersection of the substrate, aqueous phase system and corresponding gaseous environment three；The carbon nano tube dispersion liquid is applied on the liquid level of aqueous phase system, makes carbon nanotube, polymer successively on pinning to the three phase boundary line；Substrate is gradually lifted out from aqueous phase system, forms the carbon nanotube band and polymeric tapes successively arranged, and then realize the separation of carbon nanotube and polymer.Separation method of the invention is simple, it is not necessary that by heating or acids decomposing copolymer, removal polymer is more thorough, can be realized the recycling of polymer.
Description
Technical field
The present invention relates to a kind of nano-carbon material, the separation method of especially a kind of carbon nanotube and polymeric dispersant and
System belongs to carbon nanomaterial technical field.
Background technique
Single-walled carbon nanotube (SWCNT) is with its excellent physicochemical properties (super draw ratio, big specific surface area and adjustable
Unique structure and the characteristic electrons such as the band gap of section, excellent electrons and holes mobility), it is known as person in electronics most
One of material of development prospect can be applicable to next-generation field-effect film, RF transistors field.The carbon typically directly grown is received
Mitron raw material typically contains different content, different types of impurity, is the carbon nanometer of a kind of different conductive properties and different chiralitys
The mixture of pipe.It is simple with it as the dispersing agent selectively method of dispersion SWCNTs using conjugated polymer, efficiently, can scale etc.
Advantage becomes the effective ways for currently separating different conductive properties SWCNTs.The semiconductor isolated using conjugated polymer molecule
Carbon nano pipe purity is high, but also the carbon nanometer of specific even single chiral can be isolated by designing the structure of polymer
Pipe makes high performance thin film device using it on this basis.Because the one-dimensional of SWCNT makes it in electricity, optics, mechanics
And the aspect of performance such as magnetics show extremely significant anisotropy, it, can be to conjugated polymer point in order to improve device performance
Orientations are carried out from obtained high-purity SWCNT and prepare carbon nano-tube film, in the process, because of most of conjugated polymer
The non-conductor for itself belonging to electricity, so needing to remove polymer as much as possible.
Currently, removal polymer method have it is following several:
1) dispersion liquid of polymer and carbon nanotube is filtered washing, the disadvantages of the method are as follows cannot completely remove poly-
Close object dispersing agent.Because completely removing in carbon nano tube dispersion liquid existing for polymer, carbon nanotube is held because π-π interacts
" tube bank " easily is formed, subsequent thin film quality is caused to be deteriorated, and then influences device performance.Although therefore this method can be to removal
Polymer be recycled, but can only remove a part polymer；
2) third party's substance is introduced in carbon nano-tube film preparation process and polymer occurs to chemically react and removes generation
Compound, third party's material demand has specificity in this method, and corresponding third party is needed when replacing a kind of polymer
Substance, and polymer can not recycle in the method；
3) annealing makes polymer decompose removal, and the disadvantages of this method is: first, polymer generation can not inversion
Change, polymer can not recycle；Second, heat resolve polymer needs high temperature (generally at 500 DEG C or so), third, high temperature
Dioxygen oxidation carbon nanotube is avoided to cause fault of construction while decomposing copolymer；
4) by means of impregnating or being added in carbon nano tube dispersion liquid trifluoro second after acidic materials, such as film in nitric acid
Acid makes its De contamination etc., the disadvantages of this method are: operation has certain risk, polymer occurs irreversible change, causes
Polymer can not recycle.
Above method 2) -4) irreversible reaction is belonged to, be used again polymeric dispersant costly can not.Cause
This, while both polymer being removed clean there are no a kind of technology so far, moreover it is possible to which recycling benefit is carried out to polymer
With.
Summary of the invention
The main purpose of the present invention is to provide the separation methods and system of a kind of carbon nanotube and polymer, to overcome
Deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides the separation methods of a kind of carbon nanotube and polymer comprising:
Carbon nano tube dispersion liquid is provided, the carbon nano tube dispersion liquid includes carbon nanotube, as Carbon nano-tube dispersant
Polymer and organic solvent, wherein polymer and carbon nanotube by physical action in conjunction with；
The regional area of substrate is at least immersed into aqueous phase system, and in the substrate, aqueous phase system and corresponding gas phase ring
The intersection of border three forms airwater mist cooling parting line；
The carbon nano tube dispersion liquid is applied on the liquid level of aqueous phase system, make carbon nanotube therein, polymer according to
On secondary pinning to the three phase boundary line；
The substrate is gradually lifted out from aqueous phase system, forms the carbon nanotube band successively arranged and polymer strip
Band realizes the separation of carbon nanotube and polymer.
In some preferred embodiments, the separation method of the carbon nanotube and polymer includes: by the substrate to set
Determine pull rate gradually to lift out from aqueous phase system, carbon nanotube is made to form carbon nanotube layer item in substrate surface orientations
Band, and polymer is made to assemble to form polymeric tapes in substrate surface, the carbon nanotube band and polymeric tapes are distributed
In the different zones of the substrate surface.
The embodiment of the invention also provides a kind of polymer recovery processes comprising: contain while obtaining preceding method
There are the substrate and organic solvent exposure of carbon nanotube band and polymeric tapes, polymer is made to be dissolved in the organic solvent and make carbon
Nanotube remains in the substrate.
The embodiment of the invention also provides the separation system of a kind of carbon nanotube and polymer, to by carbon nanotube and with
Carbon nanotube is separated by the polymer that physical action combines, and the separation system includes:
Liquid distributing mechanism, carbon nano tube dispersion liquid to be applied on the liquid level of aqueous phase system, the carbon nanometer
Pipe dispersion liquid includes carbon nanotube, polymer and organic solvent as Carbon nano-tube dispersant, and wherein polymer is received with carbon
Mitron is combined by physical action；
Substrate at least locally immerses the aqueous phase system, and in the substrate, aqueous phase system and corresponding gas phase ring
The intersection of border three forms airwater mist cooling parting line, when the liquid that the carbon nano tube dispersion liquid is applied to aqueous phase system
When on face, carbon nanotube therein, polymer can be successively on pinnings to the three phase boundary line；And
Shift mechanism, to lift out the substrate from the aqueous phase system by setting speed, formation is successively arranged
The carbon nanotube band and polymeric tapes of cloth realize the separation of carbon nanotube and polymer.
Compared with the prior art, beneficial effects of the present invention at least that:
1) separation method of carbon nanotube provided by the invention and polymer, which is put forward for the first time, keeps polymer and carbon nanotube outstanding
Achieve the purpose that separation on bubbling through the water column, easy to operate, condition is more mild, without being decomposed by heating or acids, experiment
Risk reduces, and has the advantages of low power consuming；
2) separation method of carbon nanotube provided by the invention and polymer is the carbon nanotube of further purification high-purity,
Carbon nanotube after guaranteeing cleaning simultaneously can realize monodisperse again, in the method for filtration washing removal polymer further
Polymer is removed, removal polymer is more thorough, and is able to achieve the recycling of polymer；
3) separation method of carbon nanotube provided by the invention and polymer is no longer using specific third party's substance come needle
Certain compound is chemically reacted, applicable conjugated polymer category is wider；
4) present invention, can be by realizing carbon nano tube oriented arranging while realizing polymer and carbon nanotube separation
To achieve the purpose that improve device performance.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is that a kind of process of the separation method of carbon nanotube and polymer in an of the invention typical embodiments is illustrated
Figure.
Fig. 2 is the status diagram in an of the invention typical embodiments after the separation of a kind of carbon nanotube and polymer.
Fig. 3 is high-purity semi-conductor type single-walled carbon nano tube or single chiral carbon nanometer in a typical embodiments of the invention
The preparation flow schematic diagram of pipe dispersion liquid.
Fig. 4 a- Fig. 4 b is the high-purity semiconductor single wall of PCz polymer separation in a typical embodiments of the invention respectively
The abosrption spectrogram of carbon nanotube.
Fig. 4 c is the abosrption spectrogram of the carbon nano tube dispersion liquid dispersed again in a typical embodiments of the invention.
Fig. 5 a is the 3D focusing microscope figure of obtained polymeric tapes in the embodiment of the present invention 1.
Fig. 5 b is the 3D focusing microscope figure of obtained single streaking tube in the embodiment of the present invention 1.
Fig. 6 a- Fig. 6 h is the big model of obtained single streaking tube and polymeric tapes in the embodiment of the present invention 2 respectively
Enclose SEM figure and detail view.
Fig. 7 a is that the SEM of obtained single streaking tube and polymeric tapes schemes in the embodiment of the present invention 3.
Fig. 7 b is the SEM figure of obtained single streaking tube in the embodiment of the present invention 3, and Fig. 7 c is the enlarged drawing of Fig. 7 b.
Fig. 8 a and Fig. 8 b are the SEM figures of obtained single streaking tube in the embodiment of the present invention 4.
Fig. 9 a- Fig. 9 f is the SEM figure of obtained single streaking tube in the embodiment of the present invention 5.
Figure 10 a- Figure 10 i is the SEM figure of obtained single streaking tube in the embodiment of the present invention 6.
Figure 11 a- Figure 11 i is the SEM figure of obtained single streaking tube in the embodiment of the present invention 7.
Figure 12 a and Figure 12 b are the SEM figures of obtained single streaking tube in the embodiment of the present invention 8.
Figure 13 is the SEM figure of obtained single streaking tube in the embodiment of the present invention 9.
Figure 14 is the SEM figure of obtained single streaking tube in the embodiment of the present invention 10.
Specific embodiment
As previously mentioned, inventor is studied for a long period of time and largely practiced in view of the deficiencies in the prior art, it is able to propose this
The technical solution of invention.Technical solution of the present invention will be clearly and completely described below, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The separation method of a kind of carbon nanotube and polymer that the one aspect of the embodiment of the present invention provides comprising:
Carbon nano tube dispersion liquid is provided, the carbon nano tube dispersion liquid includes carbon nanotube, as Carbon nano-tube dispersant
Polymer and organic solvent, wherein polymer and carbon nanotube by physical action in conjunction with；
The regional area of substrate is at least immersed into aqueous phase system, and in the substrate, aqueous phase system and corresponding gas phase ring
The intersection of border three forms airwater mist cooling parting line；
The carbon nano tube dispersion liquid is applied on the liquid level of aqueous phase system, make carbon nanotube therein, polymer according to
On secondary pinning to the three phase boundary line；
The substrate is gradually lifted out from aqueous phase system, forms the carbon nanotube band successively arranged and polymer strip
Band realizes the separation of carbon nanotube and polymer.
In some preferred embodiments, the separation method of the carbon nanotube and polymer include: by the substrate with
Setting pull rate gradually lifts out from aqueous phase system, and carbon nanotube is made to form carbon nanotube item in substrate surface orientations
Band, and polymer is made to assemble to form polymeric tapes in substrate surface, the carbon nanotube band and polymeric tapes are laminated
Setting.
Further, the polymeric tapes are covered in carbon nanotube item and take.Also that is, on the substrate, the carbon
Nanotube ribbon is located at bottom, and the polymeric tapes are located at surface layer.
In the present invention, carbon nanotube preferential deposition is in substrate, even if striped is not staggered, i.e., polymeric tapes cover
In carbon nanotube strip face, also only need to wash away polymeric tapes with organic solvent, organic solvent dissolve polymer when
It waits, carbon nanotube band will not dissolve in organic solvent.
In some preferred embodiments, the separation method of the carbon nanotube and polymer include: by the substrate with
Setting pull rate gradually lifts out from aqueous phase system, and carbon nanotube is made to form carbon nanotube layer in substrate surface orientations
Band, and polymer is made to assemble to form polymeric tapes in substrate surface, the carbon nanotube band and polymeric tapes point
Cloth is in the different zones of the substrate surface.
Further, the separation method includes: the pull rate for improving the substrate, make the carbon nanotube band with
Polymeric tapes are staggered.
Further, the organic solvent is different and immiscible from the surface tension of the aqueous phase system, and boiling point is not
More than 200 DEG C.
Further, the organic solvent includes any one in halogenated alkane, aromatic hydrocarbons and halogenated aryl hydrocarbon etc. or two kinds
Above combination, but not limited to this.
Further, the halogenated alkane can selected from any one in chloroform, methylene chloride, dichloroethanes etc. or
Two or more combinations, the aromatic hydrocarbons can be selected from toluene, dimethylbenzene etc., and the halogenated aryl hydrocarbon can be selected from chlorobenzene, dichloro-benzenes
Deng, but it is not limited only to this.
Further, the aqueous phase system can be is formed by water, is also possible to aqueous solution, such as contain soluble inorganic
Object (such as inorganic salts), the aqueous solution of dissolved organic matter (such as water-soluble small organic molecule) or water with can be miscible with water
Organic solvent formed mixed system.
Further, the gaseous environment is atmospheric environment.
Among a case study on implementation, the principle of the present invention be may is that as Figure 1-Figure 2, and the present invention will include polymerization
Object and the dispersant liquid drop of carbon nanotube are scheduled on the water surface for being inserted with silicon wafer substrate, due to the effect of water surface tension, not clean
Polymer is separated with carbon nanotube；The organic solvents such as chloroform gradually vapor away at this time；In water, due to coffee ring effect,
Namely three phase boundary " pinning " effect, carbon nanotube be preferentially pinned on three phase boundary line (Air-Water face-silicon wafer substrate,
That is airwater mist cooling line), silicon wafer substrate is lifted upwards, and gradually orientations form orientation in silicon wafer substrate to carbon nanotube
Carbon nanotube band.Secondly polymer is also pinned on three phase boundary line successively, polymeric tapes is formed, in silicon wafer substrate
On, carbon nanotube band is located at bottom, and polymeric tapes are located at surface layer, improves the pull rate of silicon wafer substrate, can make to polymerize
Object band and the carbon nanotube band of orientation are staggered.Silicon wafer substrate is immersed in the stronger organic solvent of the dissolubilities such as tetrahydrofuran
In (hot toluene, chloroform etc.), so that polymer is soluble in solvent carbon nanotube at this time and still stay in silicon wafer substrate, be used for
The element manufacturings such as field effect transistor.If the present invention can carry out polymer after solvent evaporates in polymer lysate
It recycles.
As one of a preferred embodiment of the present invention, the orientations side of the carbon nanotube in the carbon nanotube band
To consistent with dip direction.
In some preferred embodiments, the pull rate is 5~65mm/min.
Further, the separation method includes: that the carbon nano tube dispersion liquid is added dropwise with the speed of 1~3 μ l/sec
On the liquid level of aqueous phase system.
Further, the syringe needle for the carbon nano tube dispersion liquid to be added dropwise is at a distance from the liquid level of the aqueous phase system
1~3mm.
Further, for be added dropwise the carbon nano tube dispersion liquid syringe needle and the substrate horizontal distance be 2~
5mm。
Further, the width of the carbon nanotube band of formation is 1~200 μm.
As one of a preferred embodiment of the present invention, the carbon nanotube is single-walled carbon nanotube or multi-wall carbon nano-tube
Pipe, the single-walled carbon nanotube preferably include metallic SWNTs, semi-conductor type single-walled carbon nano tube, single chiral list
Wall carbon nano tube etc., but not limited to this.
In the present invention, " carbon nanotube " is corresponding with " polymer ".For example, for polyethylene
The polymer such as pyrrolidones, hyper branched polymer, oligomer of phenylamine, " carbon nanotube " can be single-walled carbon nanotube,
Few-wall carbon nanotube, multi-walled carbon nanotube etc..In another example for based on carbazyl, fluorenyl, the conjugation homopolymer of thienyl or same
The polymer such as polymers, " carbon nanotube " can be semi-conductor type single-walled carbon nano tube.
In the present invention, the polymer can be used as Carbon nano-tube dispersant, by least the one of more carbon nanotubes
It is partially separated its individual size (0.4~100nm of diameter), (not agglomerating ground) in stable conditionly and make it with " isolated dispersion "
Disperse in the decentralized media such as organic solvent.Heretofore described " isolated dispersion ", refers to carbon nanotube not due to mutual
Cohesiveness and become bulk, pencil, rope form, carbon nanotube is single to disperse and existing shape in a dispersion medium in isolation
State.
In the present invention, for different types of carbon nanotube, different polymer can be chosen respectively as carbon nanotube
Dispersing agent.
For example, polyvinyl pyrrole can be used for single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube etc.
Hyper branched polymers, the oligomer of phenylamine such as alkanone, hyper branched polymer with triarylamine structure as branch point and its spread out
Biology etc. is used as corresponding Carbon nano-tube dispersant.Specifically can refering to JP200044216A, JP2005162877A,
JP200824522A、 WO2008/139839A、CN102695557B、CN101578237B、CN105645388B、
The documents such as CN105645387A, CN105642184B, CN106061894A.
For example, the applicable polymer as Carbon nano-tube dispersant, which can be, to be based on for semiconductor type carbon nano-tube
Carbazyl, fluorenyl, the conjugation homopolymer of thienyl or homopolymer, such as polythiofuran derivative, polyfluorene and/or polyfluorene derivative,
Phenylacetylene derivatives and the polymer of other structures, such as tree-like conjugated polymer etc. between poly-.More specifically, such as poly- click
Azoles, polyfluorene and polythiophene, carbazoles linear type copolymer (PCz) etc. are especially suited as point of semi-conductor type single-walled carbon nano tube
Powder.These polymer can specifically be combined by physical actions such as π-π effects with semi-conductive single-walled carbon nanotubes, and
" the isolated dispersion " for promoting semi-conductive single-walled carbon nanotubes stable in the decentralized media such as organic solvent.Further, it closes
In these polymer choose, can with reference to CN103112840B, CN105585000B, CN107456918A, CN106823983A,
CN106478927A, CN105611986B etc..
In some embodiments, the polymer includes conjugated polymer.
Further, the representative conjugated polymer for being available for carbon nanotube separation can be shown below:
Further, the material of the substrate includes rigid material, flexible material etc., and the rigid material includes silica
Piece, quartz plate or Sapphire Substrate, the flexible material include polyethylene naphthalate, polyethylene terephthalate
Or polyimides etc., but not limited to this.
Further, the substrate is hydrophobic substrate, specifically includes: the substrate is first carried out at oxygen plasma
Reason, then HMDS processing is carried out, obtain the substrate handled through hydrophobicity.For example, the substrate can be silicon wafer substrate, but unlimited
In this.
In the present invention, the semi-conductor type single-walled carbon nano tube of high-purity or the chloroform of single chiral single-walled carbon nanotube are prepared
The preparation flow figure of dispersion liquid is as shown in Figure 3: the present invention disperses using the conjugated polymer molecular selection in organic system
Then the s-SWCNT of 99.9% purity is cleaned to have obtained a part of polymer molecule and monodispersity is good by vacuum filter
S-SWCNT film, and its heavy is dispersed in the volatile organic solvent such as chloroform or toluene.The present invention is using in organic system
Conjugated polymer molecular selection disperse the semiconductor of high-purity out or single chiral single-walled carbon nanotube, then pass through vacuum
The remaining most of polymer molecule of the method removal carbon nano tube surface of filtering, further purifies the single of high-purity
Pipe, while guaranteeing that the carbon nanotube after cleaning can realize monodisperse again, it is enterprising in the method for filtration washing removal polymer
One step removes polymer, and removal polymer is more thorough, and is able to achieve the recycling of polymer.
One of case study on implementation is more highly preferred to as of the invention one, and the separation method of the carbon nanotube and polymer is specific
Steps are as follows:
1) ultrasound, centrifugation:
According to the ratio of 1:1, a certain amount of conjugated polymer molecule is accurately weighed respectively and (selects PCz, poly [9- (1-
Octylonoyl) -9H-carbazole-2,7-diyl], polycarbazole class linear type homopolymer) and original single-walled carbon nanotube it is mixed
It closes in a certain amount of dimethylbenzene (or toluene) organic solvent, making the two concentration is all 1mg/ml, and carbon nanotube includes then water
Ultrasonic disperse is carried out using ultrasonic grind instrument after bath ultrasound sufficiently dissolution polymer.Carbon pipe solution after dispersion is first in the slow-speed of revolution
Under the conditions of pre-separation, obtain after supernatant that centrifugation obtains supernatant at high speed again, as the surface extracted of polymer dispersion
The dimethylbenzene dispersion liquid of the high-purity semi-conductor type single-walled carbon nano tube of excess polymeric molecule is wrapped up.Following figure Fig. 4 a is polymerization
The semi-conductor type single-walled carbon nano tube of object PCz separation, being higher by absorption spectrum test scope from the absorption peak of PCz can be seen that
PCz content is high.Indicate the M of metal tube content11Value disappears, and illustrates that semiconductor carbon nanometer tube purity is very high.Ding study group exists
It proposes within 2014 according to UV-Vis-NIR test result (see Nanoscale 2014,6 (4): 2328-2339), uses absorption peak
RatioThe separation purity size of Large Diameter Pipeline s-SWCNTs can be evaluated, the semiconductor purity of s-SWCNTs is higher,It is worth bigger.
In Fig. 4 bIllustrate that semi-conductor type single-walled carbon nano tube purity has reached 99.9%.
2) vacuum filtration, organic solvent cleaning:
The high-purity semi-conductor type single-walled carbon nano tube or single of excessive PCz molecule is wrapped up in the surface that step 1) is obtained
The dimethylbenzene dispersion liquid of Chiral carbon nanotube, which pours into funnel, to be filtered by vacuum, and the high-purity carbon nano tube solid after separation stays
On film, then filter membrane is cleaned with a large amount of organic solvents (tetrahydrofuran, chloroform, methylene chloride etc.), removes carbon nanometer
The excessive PCz polymer molecule of pipe surface package, obtains the carbon nanotube Buckie of a certain amount of PCz polymer molecule of surface residual
Paper.
3) disperse again
The related filter membrane of the carbon nanotube Buckie paper of a certain amount of PCz polymer molecule of the surface residual that step 2) is obtained carries out
Ultrasound is re-dispersed into carbon nanotube in the easy volatile solvents such as chloroform or toluene, takes out and no longer has carbon nanotube Buckie paper
Filter membrane, obtain high-purity semi-conductor type single-walled carbon nano tube or single chiral carbon nano tube dispersion liquid.The semiconductor carbon used
Nanotube S22Absorption value is 0.2~2；Polymer PC z and carbon nanotube S22Peak value ratio is 1.5~2.8；Solvent can be chloroform,
The volatile organic solvent such as toluene.The abosrption spectrogram of the carbon nano tube dispersion liquid dispersed again c referring to fig. 4.
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying (when indoor humidity is larger, is needed to carry out silicic acid anhydride to surface: first carrying out oxygen etc.
Gas ions processing, then carry out HMDS processing) be placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, high-purity semi-conductor type single-walled carbon nano tube or single chiral carbon that step 3) is obtained
The one after another drop of injection of nanotube dispersion liquid is inserted on the water surface of silicon wafer substrate, while lifting silicon wafer substrate upwards, in silicon wafer substrate
Form the uniform smear containing single-walled carbon nanotube and polymer simultaneously.
5) uniform smear by above-mentioned simultaneously containing carbon nanotube and polymer is in organic solvent (tetrahydrofuran, chloroform, warm
Toluene etc.) in soaking and washing.Organic solution containing polymer and filtrate in step 2) are collected, the side such as revolving is passed through
Formula achievees the purpose that solvent removal to recycle polymer；If what solvent used is all toluene or dimethylbenzene, original can be directly added into
Carbon nanotube is expected to isolate the semiconductor or unidextrality single-walled carbon nanotube of high concentration.
The other side of the embodiment of the present invention additionally provides a kind of polymer recovery processes comprising: make preceding method
The substrate and organic solvent exposure for containing carbon nanotube band and polymeric tapes while acquisition, so that polymer is dissolved in this has
Solvent and remain in carbon nanotube in the substrate.
Further, the organic solvent includes any one in tetrahydrofuran, halogenated alkane, aromatic hydrocarbons and halogenated aryl hydrocarbon etc.
Kind or two or more combinations, but not limited to this.
Further, the halogenated alkane can selected from any one in chloroform, methylene chloride, dichloroethanes etc. or
Two or more combinations, the aromatic hydrocarbons can be selected from toluene, dimethylbenzene etc., and the halogenated aryl hydrocarbon can be selected from chlorobenzene, dichloro-benzenes
Deng, but it is not limited only to this.
The other side of the embodiment of the present invention additionally provides the separation system of a kind of carbon nanotube and polymer, to incite somebody to action
It carbon nanotube and is separated with carbon nanotube by the polymer in conjunction with physical action, the separation system includes:
Liquid distributing mechanism, carbon nano tube dispersion liquid to be applied on the liquid level of aqueous phase system, the carbon nanometer
Pipe dispersion liquid includes carbon nanotube, polymer and organic solvent as Carbon nano-tube dispersant, and wherein polymer is received with carbon
Mitron is combined by physical action；
Substrate at least locally immerses the aqueous phase system, and in the substrate, aqueous phase system and corresponding gas phase ring
The intersection of border three forms airwater mist cooling parting line, when the liquid that the carbon nano tube dispersion liquid is applied to aqueous phase system
When on face, carbon nanotube therein, polymer can be successively on pinnings to the three phase boundary line；And
Shift mechanism, to lift out the substrate from the aqueous phase system by setting speed, formation is successively arranged
The carbon nanotube band and polymeric tapes of cloth realize the separation of carbon nanotube and polymer.
Further, the liquid distributing mechanism uses syringe, but not limited to this.
Further, the shift mechanism is lifting instrument, but not limited to this.
Further, the gaseous environment is atmospheric environment.
Further, the aqueous phase system is contained in container, and the container is arranged on D translation platform.
In conclusion the separation method of carbon nanotube of the invention and polymer is put forward for the first time by above-mentioned technical proposal
Polymer is suspended on the water surface with carbon nanotube to achieve the purpose that separate, easy to operate, condition is more mild, without passing through
Heating or acids decompose, and experimental risk reduces, and have the advantages of low power consuming.Separation method of the invention no longer uses specific
Tripartite's substance chemically reacts to be directed to certain compound, and applicable conjugated polymer category is wider；Also, the present invention
While realizing that polymer is separated with single-walled carbon nanotube, raising device can be reached by realizing carbon nano tube oriented arranging
The purpose of part performance.Technical solution of the present invention is made more at large below in conjunction with some more specifically examples and drawings
Explanation.
Embodiment 1
Some more specific embodiments of the invention are related to the separation method of a kind of single-walled carbon nanotube and polymer,
It can specifically comprise the following steps:
1) ultrasound, centrifugation:
According to the ratio (being then mass ratio if not following illustrate) of 1:1, carbazoles linear type is accurately weighed respectively
Copolymer (refering to CN108017049A) and (the commercially available acquisition, by arc discharge method, plasma discharge of original single-walled carbon nanotube
Method, laser ablation method or chemical vapour deposition technique etc. are made) it is blended in chloroform, making the two concentration is all 1mg/ml, carbon nanometer
Pipe uses ultrasonic grind instrument to carry out ultrasonic disperse after sufficiently dissolving polymer by water bath sonicator.Carbon pipe solution after dispersion is first
The pre-separation under the conditions of slow-speed of revolution, obtains after supernatant that centrifugation obtains supernatant at high speed again, and as polymer dispersion mentions
The chloroform dispersion liquid of the high-purity semi-conductor type single-walled carbon nano tube of excessive PCz molecule is wrapped up in the surface taken.
2) vacuum filtration, organic solvent cleaning:
The chloroform of the high-purity semi-conductor type single-walled carbon nano tube of excessive PCz molecule is wrapped up in the surface that step 1) is obtained
Dispersion liquid is poured into funnel and is filtered by vacuum, and the high-purity carbon nano tube solid after separation stays on film, then with a large amount of chlorine
Imitative to clean to filter membrane, the excessive PCz molecule of removal carbon nano tube surface package obtains a certain amount of PCz molecule of surface residual
Carbon nanotube Buckie paper.
3) disperse again
The related filter membrane of the carbon nanotube Buckie paper of a certain amount of PCz molecule of the surface residual that step 2) is obtained carries out ultrasound,
It is re-dispersed into carbon nanotube in chloroform, takes out the filter membrane for no longer having carbon nanotube Buckie paper, obtain high-purity semiconductor
Type single-walled carbon nanotube dispersion liquid.The semi-conductor type single-walled carbon nano tube S used22Absorption value is 0.47；Polymer PC z receives with carbon
Mitron S22Peak value ratio is 1.5~2.8；The abosrption spectrogram of the carbon nano tube dispersion liquid dispersed again can refer to Fig. 4 c.
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, and carbon nano tube dispersion liquid rate of titration is V1=3 μ l/sec, syringe needle is apart from silicon wafer substrate
Distance about 2mm, syringe needle is apart from the water surface about 1mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 12mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Fig. 5 a shows 3D focusing microscope
The histogram of lower polymer, Fig. 5 b are the histogram of single streaking tube.Wherein, the striped of single streaking tube is wide
About 20-25 μm of degree.
Embodiment 2
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same.Difference place is: used polymerization
Object is polycarbazole derivative (refering to CN105819425A), and the solvent used is methylene chloride.
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, and carbon nano tube dispersion liquid rate of titration is V1=3 μ l/sec, syringe needle is apart from silicon wafer substrate
Distance about 3mm, syringe needle is apart from the water surface about 1mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 15mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Fig. 6 a shows obtained single wall carbon and receives
The a wide range of SEM of mitron band and polymeric tapes figure, the striped left side are carbon nanotube band, and details is shown in Fig. 6 b- Fig. 6 h, striped
The right is polymeric tapes；Wherein, about 30 μm of the width of fringe of single streaking tube.
Embodiment 3
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: it is semi-conductor type single-walled
Carbon nanotube S22Absorption value is 0.93.Difference place is: used polymer for three-dimensional tree-like conjugated compound (refering to
CN107456918A), the solvent used is chlorobenzene.
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, and carbon nano tube dispersion liquid rate of titration is V1=3 μ l/sec, syringe needle is apart from silicon wafer substrate
Distance about 2mm, syringe needle is apart from the water surface about 1mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 32mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Fig. 7 a shows obtained single wall carbon and receives
The SEM of mitron band and polymeric tapes figure, about 250 μm of the two band overall width, Fig. 7 b is the item of single streaking tube
Band figure, Fig. 7 c are the enlarged drawing of Fig. 7 b, it is seen that about 100 μm of the width of fringe of single streaking tube, illustrate polymeric tapes
It is staggered with single streaking tube, width is about 150 μm.
Embodiment 4
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: it is semi-conductor type single-walled
The concentration of carbon nano tube dispersion liquid is 24 μ g/ml, and corresponding absorption value is 0.48；Used polymer is non-linear conjugated polymerization
Object (refering to CN106478927A), the solvent used is dimethylbenzene；
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle apart from silicon wafer substrate away from
From about 5mm, syringe needle is apart from the water surface about 1mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 30mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Fig. 8 a and Fig. 8 b are single-walled carbon nanotube
The histogram of band.
Embodiment 5
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: it is semi-conductor type single-walled
The concentration of carbon nano tube dispersion liquid is 12 μ g/ml, and corresponding absorption value is 0.48；Used polymer is polyfluorene class conjugated polymers
Object (refering to CN101591219B), the solvent used is toluene；
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle apart from silicon wafer substrate away from
From about 5mm, syringe needle is apart from the water surface about 3mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 12mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Fig. 8 a and Fig. 8 b are single-walled carbon nanotube
The histogram of band.
Embodiment 6
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: it is semi-conductor type single-walled
The concentration of carbon nano tube dispersion liquid is 50 μ g/ml, and corresponding absorption value is 1.99；Used polymer is that polythiophene class conjugation is poly-
Object is closed, solvent is dichloroethanes；
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle apart from silicon wafer substrate away from
From about 2mm, syringe needle is apart from the water surface about 2mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 60mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Fig. 9 a- Fig. 9 f is single-walled carbon nanotube
The histogram of band.
Embodiment 7
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: it is semi-conductor type single-walled
The concentration of carbon nano tube dispersion liquid is 50 μ g/ml, and corresponding absorption value is 1.99；Used polymer is total for polyphenylene ethylene alkenes
Conjugated polymer；
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle apart from silicon wafer substrate away from
From about 2mm, syringe needle is apart from the water surface about 2mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 65mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Figure 10 a- Figure 10 i is single
The histogram of streaking tube.
Embodiment 8
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: it is semi-conductor type single-walled
The concentration of carbon nano tube dispersion liquid is 12 μ g/ml, and corresponding absorption value is 0.48；Used polymer is that main chain has distortion knot
The conjugated polymer (refering to CN105883749A) of structure, solvent are dichloro ethylbenzene；
4) separating single-wall carbon nanotube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the high-purity semi-conductor type single-walled carbon nano tube dispersion liquid that step 3) is obtained is one after another drop of
Injection is inserted on the water surface of silicon wafer substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle apart from silicon wafer substrate away from
From about 3mm, syringe needle is apart from the water surface about 3mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 12mm/min,
The uniform smear containing single-walled carbon nanotube and polymer simultaneously is formed in silicon wafer substrate.Figure 12 a- Figure 12 b is single
The histogram of streaking tube.
Embodiment 9
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: carbon nanometer tube material
For commercially available common carbon nanotube dust, the polymer used for polyvinylpyrrolidone, the carbon nano tube dispersion liquid of formation
Concentration is 5 μ g/ml, and corresponding absorption value is 0.2；
4) separating carbon nano-tube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the one after another drop of injection of high-purity carbon nano tube dispersion liquid that step 3) obtains is inserted with silicon wafer
On the water surface of substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle are about 2mm, needle apart from silicon wafer substrate distance
Head is apart from the water surface about 2mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 6mm/min, formed in silicon wafer substrate
Uniform smear containing carbon nanotube and polymer simultaneously.Figure 13 is the histogram of carbon nanotube band, and carbon nanotube stripes are about
It is 1 μm wide.
Embodiment 10
The present embodiment and step 1)-step 3) in embodiment 1 are almost the same, the difference is that: carbon nanometer tube material
For commercially available common carbon nanotube dust, the polymer used polymerize for the highly -branched with triarylamine structure as branch point
Object (refering to CN102695557B), the concentration of the carbon nano tube dispersion liquid of formation are 50 μ g/ml, and corresponding absorption value is 1.99；
4) separating carbon nano-tube and polymer
Silicon wafer substrate after drying is placed in similar LB slot well, deionized water is injected on surface, it is made not spill over surface.It borrows
Help microsyringe, as shown in Figure 1, the one after another drop of injection of high-purity carbon nano tube dispersion liquid that step 3) obtains is inserted with silicon wafer
On the water surface of substrate, carbon nano tube dispersion liquid rate of titration V1=3 μ l/sec, syringe needle are about 2mm, needle apart from silicon wafer substrate distance
Head is apart from the water surface about 2mm, while lifting silicon wafer substrate upwards, silicon wafer pull rate V2For 65mm/min, the shape in silicon wafer substrate
At the uniform smear simultaneously containing carbon nanotube and polymer.Figure 14 is the histogram of carbon nanotube band, carbon nanotube stripes
It is about 200 μm wide, it is staggered with polymeric tapes.
Embodiment 11:
The present embodiment is substantially the same manner as Example 10, and difference place is: the polymer choosing as Carbon nano-tube dispersant
And have at least the number-average molecular weight of 500g/mol based on functional polymer (refering to CN101578237B etc.).
Embodiment 12:
The present embodiment is substantially the same manner as Example 10, and difference place is: the polymer choosing as Carbon nano-tube dispersant
Electroactive oligomer of phenylamine of apparatus or derivatives thereof (refering to CN105645388B etc.).
In addition, inventor also refers to the mode of embodiment 1- embodiment 12, with the other originals listed in this specification
Material and condition etc. are tested, and equally realize efficiently separating for carbon nanotube and polymer, and easy to operate, condition temperature
With without being decomposed by heating or acids, experimental risk is reduced, and is consumed energy low, and removal polymer is more thorough, and is able to achieve
The recycling of polymer.
It should be noted that each technical characteristic of embodiment described above can be combined arbitrarily, to make description letter
Clean, combination not all possible to each technical characteristic in above-described embodiment is all described, as long as however, these technologies are special
Contradiction is not present in the combination of sign, 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 (20)
1. the separation method of a kind of carbon nanotube and polymer, characterized by comprising:
Carbon nano tube dispersion liquid is provided, the carbon nano tube dispersion liquid includes carbon nanotube, as the poly- of Carbon nano-tube dispersant
Close object and organic solvent, wherein polymer and carbon nanotube by physical action in conjunction with；
The regional area of substrate is at least immersed into aqueous phase system, and in the substrate, aqueous phase system and corresponding gaseous environment three
The intersection of person forms airwater mist cooling parting line；
The carbon nano tube dispersion liquid is applied on the liquid level of aqueous phase system, follows closely carbon nanotube therein, polymer successively
It pricks on the three phase boundary line；
The substrate is gradually lifted out from aqueous phase system, forms the carbon nanotube band and polymeric tapes successively arranged,
Realize the separation of carbon nanotube and polymer.
2. the separation method of carbon nanotube according to claim 1 and polymer, characterized by comprising: by the substrate
It is gradually lifted out with setting pull rate from aqueous phase system, carbon nanotube is made to form carbon nanotube in substrate surface orientations
Layer band, and polymer is made to assemble to form polymeric tapes in substrate surface, the carbon nanotube band and polymeric tapes
It is distributed in the different zones of the substrate surface.
3. the separation method of carbon nanotube according to claim 1 and polymer, it is characterised in that: the organic solvent with
The surface tension of the aqueous phase system is different and immiscible, and boiling point is no more than 200 DEG C.
4. the separation method of carbon nanotube according to claim 3 and polymer, it is characterised in that: the organic solvent packet
Include any one in halogenated alkane, aromatic hydrocarbons and halogenated aryl hydrocarbon or two or more combinations；Preferably, the halogenated alkane includes
Chloroform, methylene chloride, any one or two or more combinations in dichloroethanes；Preferably, the aromatic hydrocarbons include toluene and/
Or dimethylbenzene；Preferably, the halogenated aryl hydrocarbon includes chlorobenzene and/or dichloro-benzenes.
5. the separation method of carbon nanotube according to claim 1 and polymer, it is characterised in that: the gaseous environment is
Atmospheric environment.
6. the separation method of carbon nanotube according to claim 2 and polymer, it is characterised in that: the pull rate is
5~65mm/min.
7. the separation method of carbon nanotube according to claim 1 and polymer, characterized by comprising: with 1~3 μ l/
The carbon nano tube dispersion liquid is added dropwise on the liquid level of aqueous phase system the speed of sec.
8. the separation method of carbon nanotube according to claim 7 and polymer, characterized by comprising: for being added dropwise
The syringe needle for stating carbon nano tube dispersion liquid is 1~3mm at a distance from the liquid level of the aqueous phase system.
9. the separation method of carbon nanotube according to claim 7 and polymer, characterized by comprising: for being added dropwise
The horizontal distance of the syringe needle and the substrate of stating carbon nano tube dispersion liquid is 2~5mm.
10. the separation method of carbon nanotube according to claim 1 and polymer, it is characterised in that: the carbon nanotube
Including single wall or multi-walled carbon nanotube.
11. the separation method of carbon nanotube according to claim 10 and polymer, it is characterised in that: the single wall carbon is received
Mitron includes metallic SWNTs and/or semi-conductor type single-walled carbon nano tube；Alternatively, the single-walled carbon nanotube includes
Single chiral single-walled carbon nanotube.
12. the separation method of carbon nanotube according to claim 1 and polymer, which is characterized in that the polymer packet
Include conjugated polymer；Preferably, the conjugated polymer includes following any compound:
13. the separation method of carbon nanotube according to claim 1 and polymer, it is characterised in that: the material of the substrate
Matter includes rigid material and/or flexible material；Preferably, the rigid material includes oxidized silicon chip, quartz plate or sapphire lining
Bottom；Preferably, the flexible material includes polyethylene naphthalate, polyethylene terephthalate or polyimides.
14. a kind of polymer recovery processes, characterized by comprising: obtain any one of claim 1-13 the method
Substrate and organic solvent exposure simultaneously containing carbon nanotube band and polymeric tapes, make polymer be dissolved in the organic solvent
And remain in carbon nanotube in the substrate.
15. polymer recovery processes according to claim 14, it is characterised in that: the organic solvent includes tetrahydro furan
It mutters, any one or two or more combinations in halogenated alkane, aromatic hydrocarbons and halogenated aryl hydrocarbon；Preferably, the halogenated alkane packet
Include chloroform, methylene chloride, any one or two or more combinations in dichloroethanes；Preferably, the aromatic hydrocarbons includes toluene
And/or dimethylbenzene；Preferably, the halogenated aryl hydrocarbon includes chlorobenzene and/or dichloro-benzenes.
16. the separation system of a kind of carbon nanotube and polymer, to pass through physical action by carbon nanotube and with carbon nanotube
In conjunction with polymer separation, which is characterized in that the separation system includes:
Liquid distributing mechanism, carbon nano tube dispersion liquid to be applied on the liquid level of aqueous phase system, the carbon nanotube point
Dispersion liquid includes carbon nanotube, polymer and organic solvent as Carbon nano-tube dispersant, wherein polymer and carbon nanotube
It is combined by physical action；
Substrate at least locally immerses the aqueous phase system, and in the substrate, aqueous phase system and corresponding gaseous environment three
The intersection of person forms airwater mist cooling parting line, when on the liquid level that the carbon nano tube dispersion liquid is applied to aqueous phase system
When, carbon nanotube therein, polymer can be successively on pinnings to the three phase boundary line；And
Shift mechanism, the substrate to be lifted out from the aqueous phase system by setting speed, what formation was successively arranged
Carbon nanotube band and polymeric tapes realize the separation of carbon nanotube and polymer.
17. the separation system of carbon nanotube according to claim 16 and polymer, it is characterised in that: the liquid distribution
Mechanism uses syringe.
18. the separation system of carbon nanotube according to claim 16 and polymer, it is characterised in that: the shift mechanism
For lifting instrument.
19. the separation system of carbon nanotube according to claim 16 and polymer, it is characterised in that: the gaseous environment
For atmospheric environment.
20. the separation system of carbon nanotube according to claim 16 and polymer, it is characterised in that: the aqueous phase system
It is contained in container, the container is arranged on D translation platform.
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| CN110589804A (en) * | 2019-09-04 | 2019-12-20 | 北京华碳元芯电子科技有限责任公司 | Method for preparing carbon nano tube film by pulling method |
| CN110610946A (en) * | 2019-08-22 | 2019-12-24 | 武汉华星光电技术有限公司 | Thin film transistor, preparation method thereof and liquid crystal display panel |
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| CN110980694A (en) * | 2019-12-06 | 2020-04-10 | 中国科学院空间应用工程与技术中心 | Preparation method of ultrahigh-purity semiconductive carbon nanotube solution |
| CN111232954A (en) * | 2020-02-24 | 2020-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-purity high-concentration chiral single-walled carbon nanotube dispersion liquid, carbon nanotube film and preparation method |
| CN111232954B (en) * | 2020-02-24 | 2022-08-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-purity high-concentration chiral single-walled carbon nanotube dispersion liquid, carbon nanotube film and preparation method |
| CN111348641A (en) * | 2020-03-16 | 2020-06-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for replacing single-walled carbon nanotube solution system |
| CN111348641B (en) * | 2020-03-16 | 2022-12-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for replacing single-walled carbon nanotube solution system |
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