CN106823983B - Three-dimensional tree-like conjugated compound-carbon mano-tube composite, preparation method and application - Google Patents
Three-dimensional tree-like conjugated compound-carbon mano-tube composite, preparation method and application Download PDFInfo
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- UVNPEUJXKZFWSJ-LMTQTHQJSA-N (R)-N-[(4S)-8-[6-amino-5-[(3,3-difluoro-2-oxo-1H-pyrrolo[2,3-b]pyridin-4-yl)sulfanyl]pyrazin-2-yl]-2-oxa-8-azaspiro[4.5]decan-4-yl]-2-methylpropane-2-sulfinamide Chemical compound CC(C)(C)[S@@](=O)N[C@@H]1COCC11CCN(CC1)c1cnc(Sc2ccnc3NC(=O)C(F)(F)c23)c(N)n1 UVNPEUJXKZFWSJ-LMTQTHQJSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000005700 Stille cross coupling reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Computer Hardware Design (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention discloses a kind of tree-like conjugated compound-carbon mano-tube composites of three-dimensional, preparation method and application.The tree-like conjugated compound of three-dimensional has structure shown in formula (I) or (II):Wherein, B is that branching is conjugated link unit, selected from unit being formed by five yuan or hexa-atomic aromatic units, with branched structure；FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):M is selected from 2 or 3, and n is selected from 1,2,3 or 4.The tree-like conjugated compound of three-dimensional of the invention can be with semiconductor type carbon nano-tube selective binding, it is applicable as dispersing agent and good selective discrete nucleation type carbon nanotube, and it has good semiconducting behavior with the compound that carbon nanotube is formed, it can be applied to large-scale commercial production high-performance printable semiconductor carbon nanotube ink and high performance printed electronic device, such as the printing film transistor semiconductor device of superior performance.
Description
Technical field
Present invention relates particularly to a kind of dispersion of carbon nanotube or selective separation method, carbon mano-tube composite and corresponding
Preparation method and application, such as preparing the application in compound ink, film and semiconductor devices (such as field effect transistor),
Belong to photoelectric semiconductor material and devices field.
Background technique
Carbon nanotube is a kind of monodimension nanometer material with unique texture, has good mechanical property, and charge mobility is high,
Electric property is excellent, with flexible substrates good compatibility, the advantages such as chemical stability and thermal stability are good, in semi-conductor electronic device
In have very extensive application.
Carbon nanotube generallys use the method preparation of chemical vapor deposition (CVD), acquired under current preparation condition
Single-walled carbon nanotube be metallic SWNTs (m-SWCNTs) and semi-conductor type single-walled carbon nano tube (s-
SWCNTs mixture) significantly limits extensive use of the SWCNTs in semi-conductor electronic device.By metal single-wall carbon
Nanotube and semi-conductor type single-walled carbon nano tube are efficiently separated and are purified, and the single wall carbon with single electric conductivity is obtained
Nanotube is the key that the superior carbon nanotube semiconductor devices of processability.
According to metallic SWNTs and semi-conductor type single-walled carbon nano tube in pipe diameter size, chirality, physical chemistry
Existing fine difference in nature, related scientific research worker, which has developed, a variety of has efficacious prescriptions for isolate and purify carbon nanotube
Method, such as density gradient supercentrifugal process, fractionation, exclusion chromatography, electrophoresis, DNA cladding process and polymer encapsulation.
Polymer overmold method due to its separation method simplicity, separation quickly, can solwution method batch machining, separation selectivity
Height, separating property can fine-tune, and influence the advantages such as smaller to carbon nanotube itself proper property, so that it is had evolved into carbon and receive
An important research direction in mitron research field.
But the polymer used by the prior art for separating semiconductor type single-walled carbon nanotube is mainly line style knot
Structure.So far, using the compound molecule separating semiconductor type single wall carbon with novel three-dimensional full conjugate stereoeffect
There has been no any reports for the report of nanotube.Screening and exploitation have the conjugated compound of new space structure to efficiently separating
Semi-conductor type single-walled carbon nano tube, be effectively formed conjugated compound carbon mano-tube composite, promoted device performance have it is important
Meaning.
Summary of the invention
The main purpose of the present invention is to provide a kind of carbon nanotube dispersions or choosing based on three-dimensional tree-like conjugated compound
Selecting property separation method and application, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
Three-dimensional tree-like conjugated compound is provided in some embodiments in Selective Separation semiconductor type carbon nano-tube
Application, alternatively, purposes of the three-dimensional tree-like conjugated compound as Carbon nano-tube dispersant.
Wherein, the tree-like conjugated compound of three-dimensional has structure shown in formula (I) or (II):
Wherein, B is conjugation link unit, selected from the list with branched structure formed by five yuan or hexa-atomic aromatic units
Member,
FG is end group functionalized modification unit, contains the pyrrolo-pyrrole-dione unit as shown in formula (III) in structure:
M and n is natural integer, and m is the degree of branching of branching conjugate unit B, and value is 2 or 3, and n is three-dimensional tree-like conjugation
The algebra of compound represents repetitive unit the number of iterations in molecule, value 1,2,3 or 4.
Preferably, the carbon nanotube is selected from semiconductor type carbon nano-tube, especially semi-conductor type single-walled carbon nano tube, especially
It is Large Diameter Pipeline semi-conductor type single-walled carbon nano tube.
A kind of Carbon nano-tube dispersant is provided in some embodiments comprising the tree-like conjugation of three-dimensional closes
Object.
A kind of carbon nano tube dispersion method is provided in some embodiments comprising: take the tree-like conjugation of three-dimensional
Compound and carbon nanotube uniformly mix in solvent, form the carbon nano tube dispersion liquid of stable and uniform.
A kind of method of Selective Separation semiconductor type carbon nano-tube is provided in some embodiments comprising:
Carbon nanotube dust is added in the solution of three-dimensional tree-like conjugated compound and is sufficiently mixed, semiconductor therein is made
Type carbon nanotube is dispersed in solution,
And remove the carbon nanotube for failing to be scattered in solution.
A kind of tree-like conjugated compound-carbon mano-tube composite of three-dimensional is provided in some embodiments, and it includes carbon to receive
Mitron and the tree-like conjugated compound of three-dimensional being at least attached on carbon nanotube portion surface.
The carbon of the tree-like conjugated compound-carbon mano-tube composite of three-dimensional described in including is provided in some embodiments
Nanotube dispersion.
A kind of compound ink is provided in some embodiments comprising:
Tree-like conjugated compound-the carbon mano-tube composite of three-dimensional,
And at least one solvent, to cooperatively form stable homogeneous liquid phase with remaining component of the compound ink
Dispersion.
Preferably, the compound ink also includes organic semiconductor.
A kind of preparation method of compound ink is provided in some embodiments comprising:
The tree-like conjugated compound of three-dimensional and carbon nanotube are uniformly mixed in solvent, form uniform carbon nanotubes
Dispersion liquid,
And high speed centrifugation processing is carried out to the uniform carbon nanotubes dispersion liquid, obtained clear liquid is the composite ink
Water.
A kind of film is provided in some embodiments, and it includes the tree-like conjugated compound-carbon nanotubes of three-dimensional
Compound.
A kind of preparation method of film is provided in some embodiments comprising: it will using printing and/or coating method
The dispersion or the compound ink are applied in substrate, form the film.
Wherein, the coating and/or mode of printing include spin-coating, blade coating, slot coated, ink jet printing, silk
Wire mark brush, intaglio printing, flexographic printing, any one or two or more combinations in soft impact transfer printing mode, but not limited to this.
Further, the preparation method further includes film post-processing step, and the film post-processing step includes clear
It washes and annealing operation.
A kind of device is provided in some embodiments, it includes the described tree-like conjugated compound of three-dimensional, described three
Tie up tree-like conjugated compound-carbon mano-tube composite or the film.
Preferably, described device is selected from semiconductor device.
Preferably, described device includes field effect transistor, and the active layer of the field effect transistor includes described three
Tie up tree-like conjugated compound-carbon mano-tube composite or the film.
Further, the field effect transistor is mainly by source electrode, drain electrode, gate electrode, dielectric layer and active layer structure
At.
Compared with prior art, the present invention at least has the advantages that
1) the novel tree-like compound molecule with three-dimensional conjugate space stereochemical structure is provided, molecular structure is single really
It is fixed, the otherness between polymer batch, favorable repeatability can be overcome, and be applicable as dispersing agent and good selectivity dispersion
Semiconductor type carbon nano-tube, especially semi-conductor type single-walled carbon nano tube；
It 2), can also be effectively real by adjusting solvent type, carbon nanotube concentration and three-dimensional tree-like conjugated compound concentration etc.
The mesh of the novel dendrimers selective coated separation Large Diameter Pipeline semiconductor carbon nanometer tube of existing three-dimensional conjugate space stereochemical structure
's；
3) the tree-like conjugated compound-carbon mano-tube composite processing technology of three-dimensional provided is simple, required chemical combination object amount phase
To less, the time used in separation process is short, centrifugal speed is low, low in cost；
4) printing film that can construct superior performance using the obtained Large Diameter Pipeline semiconductor carbon nanometer tube of the method for the present invention is brilliant
Body pipe semiconductor devices；
5) the tree-like conjugated compound-carbon mano-tube composite of three-dimensional of the invention has good semiconducting behavior, can quilt
Applied to large-scale commercial production high-performance printable semiconductor carbon nanotube ink and high performance printed electronic device.
Detailed description of the invention
Fig. 1 and Fig. 2 be respectively the embodiment of the present invention 4, embodiment 5 (P2-CNT, three-dimensional tree-like conjugated compound (6T-DPP,
9T-DPP), toluene) obtained semiconductor carbon nanometer tube (hereinafter referred to as " S-CNT ") abosrption spectrogram；
Fig. 3 and Fig. 4 be respectively the embodiment of the present invention 6, embodiment 7 (P2-CNT, three-dimensional tree-like conjugated compound (6T-DPP,
9T-DPP), toluene) Raman spectrogram of obtained S-CNT under different test conditions；
Fig. 5 and Fig. 6 is the embodiment of the present invention 1 (P2-CNT, three-dimensional tree-like conjugated compound (9T-DPP), toluene) structure respectively
The performance chart for the thin film transistor (TFT) built.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
One aspect of the present invention provides a kind of tree-like conjugated compound of three-dimensional, with shown in formula (I) or (II)
Structure:
Wherein, B is to be conjugated link unit, the unit with branched structure formed by five yuan or hexa-atomic aromatic units,
FG is end group functionalized modification unit, contains the pyrrolo-pyrrole-dione unit as shown in formula (III) in structure:
M and n is natural integer, and m is the degree of branching of branching conjugate unit B, and value is 2 or 3, and n is three-dimensional tree-like conjugation
The algebra of compound represents repetitive unit the number of iterations in molecule, value 1,2,3 or 4.
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
Wherein, pyrrolo-pyrrole-dione (DPP) structural unit FG has raw material cheap and easy to get, and by force by electronic capability, height rubs
Your extinction coefficient, high charge mobility and is easy to modify the advantages that adjusting physical and chemical performance by directed chemical.
Preferably, the above-mentioned end group functionalized modification unit F G containing pyrrolo-pyrrole-dione unit is in such as flowering structure
One kind, but be not limited to following structures:
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
In some embodiments, also draw in the above-mentioned end group functionalized modification unit F G containing pyrrolo-pyrrole-dione unit
Enter to hold the blocking units of position, is passivated the reactivity of one end.Specific blocking units can be as follows, but is not limited to following structures:
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
By taking above-mentioned (III-1) unit as an example, in some embodiments, the asymmetric FG functionalized modification of blocking units is combined
The structure of unit can be selected from but not limited to following structures:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
In some embodiments, in order to construct with the single deterministic tree-like conjugated compound of three-dimensional of molecular structure, this
The conjugation of branching provided by inventing link unit B has (IV-1), (IV-2), one in structure described in (IV-3) or (IV-4)
Kind:
Wherein, Y is selected from phenyl ring or thiophene unit, and D is selected from phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units
Formed condensed ring unit or by 2~4 five yuan or hexa-atomic aromatic units is formed be conjugated short chain units.
Wherein, Y can be selected from phenyl ring, can form different branched structures by the substitution of different location, comprising:
It can be constructed by repeating above-mentioned branched structure unit IV-1-1 such as formula (IV-1-1-G1)-(IV-1-1-G3) institute
The following branching conjugation construction unit shown, such as:
The wherein active site of peripheral benzene ring units and the functionalized modification unit (FG) with pyrrolo-pyrrole-dione unit
It is connected, and the active site on the phenyl ring in kernel is hydrogen atom (as shown in formula (I)) or they are connected therebetween
Form the compound molecule with structure shown in formula (II).
For example, the molecular structure with formula (I) and formula (II) based on above-mentioned IV-1-1-G3 unit is as follows:
Following branching conjugation construction unit can also be constructed by repeating above-mentioned branched structure unit (formula (IV-2-1)),
Such as:
Wherein the active site of peripheral benzene ring units is connected with the functionalized modification unit with pyrrolo-pyrrole-dione unit
It connects, and the active site on the phenyl ring in kernel is hydrogen atom (as shown in formula (I)) or they are connected to form therebetween
Compound molecule with structure shown in formula (II).
For example, the molecular structure with formula (I) and formula (II) based on above-mentioned IV-2-1-G3 unit is as follows:
Y can also be selected from thiophene, and by α, the disubstituted mode of β-is formed with branched structure shown in formula (IV-1-2):
It can be constructed using above-mentioned branched structure unit IV-1-2 is repeated such as formula (IV-1-2-G1)~formula (IV-1-2-
G3 branching shown in) is conjugated construction unit, such as:
Wherein the alpha-position of peripheral thiophene unit is connected with the functionalized modification unit with pyrrolo-pyrrole-dione unit, and
The thiophene alpha-position of kernel is hydrogen atom (as shown in formula (I)) or they are connected to form therebetween with knot shown in formula (II)
The compound molecule of structure.
For example, the molecular structure with formula (I) and formula (II) based on above-mentioned IV-1-2-G4 unit is as follows:
In order to reduce the effect of the steric hindrance between intramolecular difference group unit, can also draw between repetitive unit Y
Enter conjugate unit D to improve the distance between repetitive unit Y.
The conjugate unit D unit can be selected from phenyl ring, thiphene ring, can also be selected from by 2~5 five yuan or hexa-atomic virtue
Fragrant unit forms condensed ring unit, including but not limited to flowering structure:
Wherein, X1=S or O, X2The miscellaneous alkane of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20
Base, R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
Or D is selected from and forms conjugation short chain units by 2~4 five or hexa-atomic aromatic units, it is including but not limited to following
Structure:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkane of C1~C20
Base.
Preferred Y and D unit are thiophene unit.Corresponding branching conjugation link unit B has the following structure:
In formula, outer end thiophene alpha-position (p-a and p-b) is connected with end group functionalized modification unit F G, or by with inner end thiophene
Pheno alpha-position (c-a), which is connected to form, is conjugated link unit with formula (V-G2), (V-G3), or the high algebra branching of (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with the end group modification unit with pyrrolo-pyrrole-dione unit, and
The thiophene alpha-position of kernel is hydrogen atom (structural formula I) or they are connected to form therebetween the molecule with formula II.
To hold position FG for the structural unit with III-1-EG1, branched structure B is that V is, number of iterations n=2 and n=3,
The molecular structure of conjugated compound (the i.e. described tree-like conjugated compound of three-dimensional) constructed by the present invention with branched structure
Include:
One aspect of the present invention additionally provides the method for synthesizing the tree-like conjugated compound of three-dimensional comprising: it uses
Metal catalytic condensation reaction prepares the tree-like conjugated compound of three-dimensional.Wherein, the metal catalytic condensation reaction includes
Suzuki condensation, stille condensation etc., but not limited to this.
In some embodiments, there is the tree-like conjugated compound of three-dimensional shown in aforementioned formula (I) can pass through reaction system (1)
The method of the reaction step of expression prepares synthesis.
Reaction system (1):
In above formula, m is the degree of branching of branching conjugate unit B, and value is 2 or 3；N, n1, n2 are three-dimensional tree-like conjugation
The algebra for closing object, represents repetitive unit the number of iterations in molecule, and value is the integer more than or equal to 0.N1≤1, n2≤0, n=
n1+n2.As n2=0, the structure of formula (b) such as formula (b, n2=0) shown in.
V2-FG
(b, n2=0)
In some embodiments, have the tree-like conjugated compound of three-dimensional shown in formula (II) can be by including with reaction system
(2) method of the reaction step indicated prepares synthesis.
Reaction system (2):
In above formula, m is the degree of branching of branching conjugate unit B, and value is 2 or 3；N, n1, n2 are three-dimensional tree-like conjugation
The algebra for closing object, represents repetitive unit the number of iterations in molecule, and value is the integer more than or equal to 0, n1≤1, n2≤0, n=
n1+n2.As n2=0, the structure of formula (b) such as formula (b, n2=0) shown in.
V2-FG
(b, n2=0)
In some embodiments, have the tree-like conjugated compound of three-dimensional shown in formula (II) can also be by including with reactant
It is the method preparation synthesis for the reaction step that (3) indicate.
Reaction system (3):
In above formula, m is the degree of branching of branching conjugate unit B, and value is 2 or 3；N is three-dimensional tree-like conjugated compound
Algebra represents repetitive unit the number of iterations in molecule, value 1,2,3 or 4.
Above-mentioned each reaction system and respective reaction step will be described in detail as follows.
In above-mentioned each reaction system and reaction step, the dendroid conjugated compound with reaction active groups V1 point
Son with have reaction active groups V2Dendroid conjugated compound molecule reaction be by Suzuki cross-coupling reaction or
What stille cross-coupling reaction was realized.
For example, previous reaction active group V1And V2Following three groups of active reactive groups can be selected from, but are not limited to
This.
Active reactive group group 1:
- F ,-Br ,-I.
Active reactive group group 2:
R4Selected from the linear or branched alkyl group for being 1-4 containing carbon number.
Active reactive group group 3:
R5Selected from the linear or branched alkyl group for being 1-4 containing carbon number.
In some embodiments, when preparing the three-dimensional tree-like conjugated compound using Suzuki method of condensing, V1And V2
Combination (V1, V2) include (selected from active reactive group group 1, selected from active reactive group group 3) or (be selected from active reactive group
Group 3 is selected from active reactive group group 1).
In some embodiments, when using stille method of condensing prepare compound, V1And V2Combination (V1, V2) packet
It includes and (selected from active reactive group group 1, is selected from active reactive group group 2) or (active reactive group group 2 is selected from, selected from active anti-
Answer group group 1).
More preferably, V1Selected from-Br ,-I；V2The active reactive group shown in the formula (g).
The metallic catalyst refers to soluble metal palladium complex, such as may be selected from but not limited to: Pd
(PPh3)4, Pd (OAc)2, Pd2(dba)3, Pd2(dba)3·CHCl3, Pd (dppf) Cl2, preferred catalyst can be Pd
(PPh3)4, Pd2(dba)3, Pd2(dba)3·CHCl3。
In some embodiments, when selection is free of the Pd catalyst Pd of ligand2(dba)3Or Pd2(dba)3·CHCl3When, it urges
It also needs to add phosphorus ligand in change system, to improve reaction efficiency, the phosphorus ligand includes but is not limited to: PPh3Or HP
(tBu)3BF4, preferably, the molar ratio of such as phosphorus ligand and catalyst Pd atom can be 2:1.
In some embodiments, it when selecting Suzuki catalyzing and condensing preparation method, needs to be added in reaction system inorganic
Metal aqueous slkali.The metal base includes carbonate, such as: Na2CO3, NaHCO3, K2CO3, KHCO3；Phosphate, such as: K3PO4,
K2HPO4；Carboxylate, such as: KOAc, NaOAc, but it is not limited to this.
Wherein, applicable solvent may include but be not limited to toluene, glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane,
DMF, DMSO, methylene chloride, chloroform.Preferred solvent can be tetrahydrofuran or chloroform, but not limited to this.
Another aspect of the present invention additionally provides a kind of tree-like conjugated compound-carbon mano-tube composite of three-dimensional, master
It to be made of carbon nanotube and the tree-like conjugated compound of three-dimensional for being attached to carbon nano tube surface.
The tree-like conjugated compound of three-dimensional of the invention is to include pyrrolo-pyrrole-dione unit with three-dimensional tree-like vertical
The non-linear conjugated compound of body structure, wherein the introducing of the B group with certain space gauche conformation structure is that acquisition is non-thread
Property dendroid conjugated compound key, these three-dimensional tree-like conjugated compounds have the dendritic structure of distortion in space, should
The twist structured conjugated compound of dendroid can effectively coat on the carbon nanotubes, so that between polymer and carbon nanotube
Interaction force enhanced, the stability of compound is also largely increased.
Another aspect of the present invention additionally provides the tree-like conjugated compound of three-dimensional as Carbon nano-tube dispersant
Purposes, especially as the purposes of semiconductor type carbon nano-tube selectivity dispersing agent, wherein the carbon nanotube is selected from semiconductor
Type carbon nanotube, especially semi-conductor type single-walled carbon nano tube, especially Large Diameter Pipeline semi-conductor type single-walled carbon nano tube.
Another aspect of the present invention additionally provides a kind of carbon nano tube dispersion method comprising: take the three-dimensional tree
Shape conjugated compound and carbon nanotube uniformly mix in solvent, form the carbon nano tube dispersion liquid of stable and uniform.
Another aspect of the present invention additionally provides a kind of method of Selective Separation semiconductor type carbon nano-tube, packet
It includes:
Carbon nanotube dust is added in the solution of three-dimensional tree-like conjugated compound and is sufficiently mixed, semiconductor therein is made
Type carbon nanotube is dispersed in solution,
And remove the carbon nanotube for failing to be scattered in solution.
Wherein, the carbon nanotube dust can be the carbon nanotube dust of commercial sources acquisition or utilize known in the art
The carbon nanotube dust for preparing of various modes, usually may include semiconductor type carbon nano-tube and metal mold carbon nanotube
Deng.
Wherein, the solvent used in the solution can dissolve selected from any but not destroy the tree-like conjugation of three-dimensional
The solvent of molecular structure of compounds, especially organic solvent, for example, chloroform, tetrahydrofuran, toluene, ortho-xylene, to two
Toluene, meta-xylene, acetone, trimethylbenzene, chlorobenzene and dichloro-benzenes etc..
In some embodiments, the method for the Selective Separation semiconductor type carbon nano-tube specifically includes:
Carbon nanotube dust is added in the solution of three-dimensional tree-like conjugated compound and is sufficiently mixed, semiconductor therein is made
Type carbon nanotube forms compound in conjunction with three-dimensional tree-like conjugated compound and is dispersed in solution, and makes wherein substantially not
The metal mold carbon nanotube sedimentation that can be combined with three-dimensional tree-like conjugated compound is removed not in a manner of being centrifuged or filtering etc. later
The metal mold carbon nanotube etc. that can be scattered in solution.
It includes that the tree-like conjugated compound-carbon nanotube of three-dimensional is compound that another aspect of the present invention, which additionally provides,
The nanotube dispersion of object.
More specifically, for example, it includes following components the present invention provides a kind of compound ink:
(a) at least one tree-like conjugated compound of three-dimensional,
(b) at least one carbon nanotube,
(c) at least one solvent, special organic solvent.
The tree-like conjugated compound of three-dimensional with structural formula I or formula II in compound ink provided by the present invention can
It is effectively coated on formation supermolecule composite construction on the tube wall of semiconductor type carbon nano-tube, semiconductor type carbon nano-tube is improved and exists
Dispersibility in organic solvent, so that the discrete nucleation type single-walled carbon nanotube of selectivity, obtains enriched semiconductor type single wall
The finely dispersed ink of carbon nanotube.
Straight chain contained by the tree-like conjugated compound of three-dimensional in aforementioned compound ink with structural formula I or formula II or
Branched alkyl units can also effectively improve three-dimensional tree-like conjugated compound dissolubility in organic solvent, adjust three-dimensional tree
Interaction between shape conjugated compound and carbon nanotube, the surface defect for reducing carbon nanotube layer in film, improve and carry
Sub- concentration and carrier mobility etc. are flowed, to adjust the tree-like conjugated compound film of carbon nanotube-three-dimensional to electrode interface
Modification performance, and then improve optimization semiconductor devices electric property.
Commercialization Large Diameter Pipeline P2 single-walled carbon nanotube can be used in carbon nanotube in compound ink provided by the present invention, that is, adopts
The Large Diameter Pipeline single-walled carbon nanotube obtained with commercialization arc discharge method.
The organic solvent used in compound ink provided by the present invention can preferably dissolve three-dimensional tree-like conjugation and close
Object and the organic solvent for itself being unable to dispersing Nano carbon tubes, for example, can be selected from chloroform, tetrahydrofuran, toluene, ortho-xylene,
Any one in paraxylene and meta-xylene or two kinds and two or more combinations, but not limited to this.
It, can also be comprising in acetone, trimethylbenzene, chlorobenzene, dichloro-benzenes in solvent of the invention in some case study on implementation
It is one or two kinds of and two or more, for dispersing and stablizing the compound ink configured, improve the processing for configuring compound ink
Performance.
In compound ink provided by the present invention, due to the selective coated effect of three-dimensional tree-like conjugated compound, energy
Enough dispersions for largely improving semi-conductor type single-walled carbon nano tube in three-dimensional tree-like conjugated compound and organic solvent
Property, while will not occur significantly to reunite, so as to keep the original mechanics of semi-conductor type single-walled carbon nano tube and electricity
Effectively stablize prepared ink under the premise of performance.
In compound ink provided by the present invention, weight/body of three-dimensional tree-like conjugated compound-carbon mano-tube composite
Product concentration is preferably 0.01~20mg/mL.Lower solid content make compound processing preparation process in complex deposits amount not
Foot, semi-conductor type single-walled carbon nano tube cannot be attached and fixed to substrate surface well, and higher solids level concentration is easy to lead
It causes solid to be precipitated, is unfavorable for the stable dispersion of ink.
In compound ink provided by the present invention, the Mixing ratio by weight of three-dimensional tree-like conjugated compound and carbon nanotube is excellent
It is selected as 1:0.1~1:10, the polymer of too high amount will lead to the residual of polymer in the devices, weaken semi-conductor type single-walled carbon
Effect of the nanotube in institute's processing device in terms of charge transmission, too low polymer ratio are difficult to effectively adhere on substrate
Fixed semi-conductor type single-walled carbon nano tube leads to not form fine and close carbon nanotube network in channels, to influence
The high efficiency of transmission of charge, reduces the electric property of transistor in institute's processing device.More preferably three-dimensional tree-like conjugated compound
Mixing ratio by weight example with carbon nanotube is preferably 1:0.2~1:5.
The present invention also provides the preparation methods of the compound ink.Wherein, the compound ink can use following two
Kind preparation method.
For example, the tree-like conjugated compound of three-dimensional is first dissolved at least one solvent, then in temperature≤0 DEG C
Under conditions of, the commercialization Large Diameter Pipeline P2 single-walled carbon nanotube is dispersed in the tree-like conjugation of three-dimensional of first step preparation
It in compound solution, is finally centrifuged at a high speed in short-term again, isolates supernatant liquor and obtain the big of enriched semiconductor type
The ink solution of the business carbon nano tube of caliber.
For example, first the described tree-like conjugated compound of three-dimensional is mixed with other organic semiconducting materials, then one
With solvent in organic solvent, then ultrasound is evenly dispersed under conditions of temperature≤0 DEG C, finally carries out high speed centrifugation in short-term again
Separation, isolates supernatant liquor and prepares to form ink.
The organic solvent at least can be selected from chloroform, tetrahydrofuran, toluene, ortho-xylene, paraxylene or
Any one in meta-xylene or two kinds and two or more combinations, but not limited to this.
Obviously, the preparation process of the compound ink is simple, low in cost, easy to operate, is easy to batch and prepares.
Wherein, the selection of solvent needs dispersion performance, three-dimensional tree-like conjugation in conjunction with carbon nanotube in different solvents
Close solubility property and subsequent three-dimensional tree-like conjugated compound-carbon mano-tube composite deposition process pair of the object in different solvents
The requirement of solvent carries out comprehensive selection.
Wherein, the polarity and dissolubility of solvent are to three-dimensional tree-like conjugated compound separating semiconductor type single-walled carbon nanotube
There is large effect.For example, although chloroform has extraordinary dissolubility to single-walled carbon nanotube, the carbon largely dispersed
Nanotube is existed with the state gathered into bundles in the solution, can not achieve the selectivity of single semi-conductor type single-walled carbon nano tube
Dispersion, to affect its application in terms of device fabrication preparation.It is more excellent for preparing carbon nano-tube film transistor
The organic solvent of choosing includes that toluene, ortho-xylene, paraxylene and meta-xylene etc. itself are unable to the organic of dispersing Nano carbon tubes
Solvent, but these solvents have good dissolubility to three-dimensional tree-like conjugated compound, in these solvents three-dimensional tree-like conjugation
It is compound that the cladding semi-conductor type single-walled carbon nano tube of the conjunction object property of can choose forms three-dimensional tree-like conjugated compound-carbon nanotube
Object realizes the purpose of Selective Separation semi-conductor type single-walled carbon nano tube, and it is brilliant that acquisition can be used for preparing processing carbon nano tube film
The ink solution of the business carbon nano tube of the Large Diameter Pipeline of the enriched semiconductor type of body pipe.
In addition, the difference of selected solvent, will affect the surface tension of ink to a certain extent, so influence ink with
The contact performance of substrate, to influence to process the performance of the carbon nano-tube film transistor of preparation.Preferably, described organic molten
Agent can be selected from chloroform, tetrahydrofuran, toluene, ortho-xylene, paraxylene, meta-xylene, chloroform and tetrahydro furan
Any one in muttering or two kinds and two or more combinations, but not limited to this.
The high speed centrifugation operation used in the preparation process of aforementioned compound ink, preferred embodiment are as follows: centrifugation speed
Degree is greater than 8000rpm, and centrifugal speed is preferably controlled in 10000~30000rpm；Centrifugation time is in 20min or more, centrifugation time
It is preferably controlled to 30~100min.
One aspect of the present invention additionally provides a kind of film, wherein receiving comprising the tree-like conjugated compound-carbon of the three-dimensional
Mitron compound.
Further, the present invention also provides a kind of straightforward procedures for preparing the film, for example, using described compound
Ink is prepared by the methods of being coated with or printing deposition.The coating method includes dip coated, drippage coating, rotation
Turn coating, blade coating, slot coated etc.；The mode of printing includes inkjet printing, silk-screen printing, intaglio printing, air-flow
Spray printing, soft impact transfer printing etc., but not limited to this.
During actual deposition prepares laminated film, the film is usually deposited on base material.It is described
Base material include: silicon wafer, glass, plastics, paper and sheet metal, such as: stainless steel, aluminium foil, but not limited to this.
The printer of squash type marking ink can be selected in printer in aforementioned inkjet printing, as Dimatrix 2831,
3000,5005, MicroFab and aerosol ink-jet printer etc., but not limited to this.
During aforementioned printing prepares laminated film, in the ink concentration of carbon nanotube be preferably 0.0001~
1mg/mL。
The present invention also provides a kind of method for subsequent processing of film, the subsequent treatment process include solvent cleaning and
Annealing etc..
In solvent cleaning process above-mentioned, solvent can be selected from chloroform, tetrahydrofuran, toluene, ortho-xylene, to two
Any one in toluene, meta-xylene, chloroform and tetrahydrofuran or two kinds and two or more combinations, but be not limited to
This.
In annealing operation above-mentioned, at 200 DEG C hereinafter, preferably 25~120 DEG C, annealing time is the annealing temperature of use
30~120min, preferably 30~60min.
One aspect of the present invention additionally provides a kind of device, and it includes the tree-like conjugated compound-carbon of three-dimensional to receive
Mitron compound or the film.
Among some embodiments, described device can be semiconductor device, semiconductor material layer (such as it is active
Layer) it include the film.
Further, the semiconductor device can be transistor, phase inverter etc., but not limited to this.
For example, the present invention also provides a kind of field effect transistors, mainly by source electrode, drain electrode, gate electrode, dielectric
Layer and active layer are constituted, and the active layer contains the tree-like conjugated compound-carbon mano-tube composite or described of three-dimensional
Film.
Further, the field effect transistor is thin film transistor (TFT), and it is tree-like to can use the carbon nanotube-three-dimensional
The compound ink of conjugated compound, deposition side built-up by the methods of drop coating, spin coating, dip-coating, intaglio printing and inkjet printing
Formula multiplicity, processing technology are simple.
For example, the present invention provides the tree-like conjugated compound-carbon mano-tube composites of the three-dimensional as thin film transistor (TFT)
Active layer.
The present invention can be applied to large-scale commercial production high-performance printable semiconductor carbon nanotube ink and high property
The printed electronic device of energy.
To make the present invention it is more readily appreciated that doing further below in conjunction with several embodiments to technical solution of the present invention
Illustrate explanation, it is noted that these embodiments are only to of the invention exemplary illustrated, wherein used various products
Structural parameters, various reaction partners and process conditions are more typical examples, but pass through inventor's a large number of experiments
Verifying, other types of reaction partner and other process conditions listed by above are also applicable, and also reachable
The technical effect claimed at the present invention.Technical solution of the present invention is made into one below in conjunction with attached drawing and several preferred embodiments
The explanation of step.
Some more typical tree-like conjugated compounds of three-dimensional involved in following examples, structural formula difference are as follows:
In these typical three-dimensional tree-like conjugated compounds, the tree-like oligo-thiophenes core with branch structure constructs single
Member can refer to document (Chem.Eur.J.2012,18,12880-12901) synthesis.
The specific synthesis technology of these typical three-dimensional tree-like conjugated compounds above-mentioned can refering to hereafter, (7), (8),
(9) ,-C in (10), (11) and (16)8H17For ethylhexyl, (12), (13), (14) ,-C in (15)20H41For octyl ten
Dialkyl group.
(1) synthesis of compound 3
It weighs (compound 1) (2.0g, 2.13mmol), compound 2 (1.5g, 5.1mmol), Pd2(dba)3.CHCl3
(44mg,43μmol),HP(tBu)3BF4Two mouthfuls of round-bottomed flasks of 250mL are added in (25mg, 86 μm of ol) under nitrogen atmosphere, to above-mentioned two
The THF (150mL) of the degassing process of degassing process is added in mouth bottle, K is then added dropwise into reaction system again2CO3Aqueous solution
(1M, 12.0mL, 12.0mmol), ambient temperature overnight stirring.Reaction system gradually becomes bluish violet.It, first will be in solution after 24 hours
Most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collect organic phase, with anhydrous sodium sulfate dry it is organic
Phase, filtering, rotary evaporation remove solvent, and with silica gel chromatographic column separation product, eluent is methylene chloride: n-hexane (1:4) obtains
To 2.1g blue solid (compound 3), yield 94%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=8.92 (d, J=4.04Hz, 1H), δ=8.84 (d, J=3.04Hz, 1H),
7.60 (d, J=4.40Hz, 1H), 7.24-7.27 (m, 1H), 7.22 (d, J=4.12Hz, 1H), 7.14 (d, J=3.44Hz,
1H), 6.74 (d, J=3.60Hz, 1H), 4.03 (d, J=2.08Hz, 2H), 4.01 (d, J=2.00Hz, 2H), 2.80-2.84
(m,2H),1.91-1.96(m,2H),1.66-1.74(m,2H),1.21-1.34(m；70H),0.83-0.92ppm(m,15H).
MALDI-TOF MS:m/z calcd for C64H102N2O2S3:1026.7,found:1026.0(matrix:
DCTB)。
(2) synthesis of compound 4
[Ir (OMe) (COD)] is weighed in glove box2(62mg, 94 μm of ol), HBPin (600mg, 4.68mmol),
Dtbpy (50mg, 186 μm of ol), is sufficiently stirred, is sufficiently mixed three kinds of substances, forms catalyst system.Weigh Compound 3
(2.4g, 2.34mmol) is added in 100mL two mouth flask, and the dry THF of 50mL is added into the two mouth flask.By caltalyst
System is added in the two mouth flask for filling compound 3, reacts 4 hours at 50 DEG C.When reaction is cooled to room temperature, solvent is rotated
Obtain crude product.Crude product obtains compound 4 (2.3g), yield 85% by silica gel chromatograph post separation.Its characterize data is such as
Under:
1H NMR(CDCl3, 400MHz): δ=8.95 (d, J=4.16Hz, 1H), δ=8.85 (d, J=3.84Hz, 1H),
7.70 (d, J=3.88Hz, 1H), 7.23 (d, J=4.16Hz, 1H), 7.14 (d, J=3.56Hz, 1H), 6.74 (d, J=
3.64Hz,1H),4.01-4.07(m,4H),2.80-2.84(m,2H),1.89-1.96(m,2H),1.66-1.74(m,2H),
1.37(s,12H),1.21-1.34(m；70H),0.83-0.92ppm(m,15H).
MALDI-TOF MS:m/z calcd for C64H102N2O2S3:1151.8,found:1151.6(matrix:
DCTB)。
(3) synthesis of compound 6 (G1-Dendron-FG1-EG2)
It weighs (compound 5) (100mg, 200 μm of ol), compound 4 (530mg, 460 μm of ol), Pd2(dba)3·CHCl3
(10mg,10μmol),HP(t-Bu)3·BF4Two mouthfuls of round-bottomed flasks of 25mL, Xiang Shangshu is added in (8mg, 27 μm of ol) under nitrogen atmosphere
The THF (10.0mL) of the degassing process of degassing process is added in two-mouth bottle, K is then added dropwise into reaction system again2CO3Water
Solution (1M, 1.2mL, 1.2mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.After 24 hours, first by solution
In most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collect organic phase, with anhydrous sodium sulfate dry have
Machine phase, filtering, rotary evaporation remove solvent, and with silica gel chromatographic column separation product, eluent is methylene chloride: n-hexane (1:9),
Obtain 372mg blue solid (compound 6), yield 81%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=8.94 (d, J=2.92Hz, 1H), δ=8.93 (d, J=2.96Hz, 1H),
8.89 (t, J=4.48Hz, 2H), 7.34 (d, J=5.28Hz, 1H), 7.27 (d, J=1.04Hz, 1H), 7.26 (d, J=
1.04Hz, 1H), 7.23 (d, J=3.80Hz, 1H), 7.21 (d, J=4.24Hz, 3H), 7.19 (d, J=5.28Hz, 1H),
7.13 (d, J=3.56Hz, 2H), 7.11 (d, J=3.84Hz, 1H), 7.05 (d, J=3.84Hz, 1H), 6.73 (d, J=
3.64Hz, 2H), 4.02 (d, J=7.00Hz, 8H), 2.81 (t, J=7.56Hz, 4H), 1.94-1.99 (m, 4H), 1.66-
1.73(m,4H),1.21-1.34(m；140H),0.81-0.93ppm(m,30H).
MALDI-TOF MS:m/z calcd for C140H208N4O4S9:2297.3,found:2297.6(matrix:
DCTB)。
(4) synthesis of compound 8 (G1-Dendrimer-FG1-EG2)
Weigh Compound 4 (630mg, 546 μm of ol), compound 7 (100mg, 124 μm of ol), [Pd2 (dba)3]·CHCl3
(10mg,10μmol),and HP(tBu)3·BF4Two mouthfuls of round-bottomed flasks of 50mL are added in (8mg, 27 μm of ol) under nitrogen atmosphere, upwards
The THF (25.0mL) that the degassing process of degassing process is added in two-mouth bottle is stated, K is then added dropwise into reaction system again2CO3
Aqueous solution (1M, 2.0mL, 2.0mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.It, first will be molten after 24 hours
Most of solvent in liquid is concentrated by evaporation, then uses methylene chloride/water extraction solution, collects organic phase, is dried with anhydrous sodium sulfate
Organic phase, filtering, rotary evaporation removes solvent, divides with silica gel chromatograph post separation small molecular weight impurity, then with gel chromatography column purification
From obtaining 460mg blue solid (compound 8), yield 81%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=8.81 (d, J=3.56Hz, 4H), δ=8.76 (dd, J=4.24Hz, 4H),
7.15-7.19 (m, 10H), 7.07-7.09 (m, 8H), 7.04 (d, J=3.12Hz, 4H), 6.66 (d, J=3.40Hz, 4H),
3.90(br,16H),2.73(br,8H),1.85(br,8H),1.57-1.65(m,8H),1.21-1.34(m；280H),0.72-
0.84ppm(m,60H)。
MALDI-TOF MS:m/z calcd for C280H414N8O8S18:4592.7,found:4592.3(matrix:
DCTB)。
(5) synthesis of compound 10 (G2-Dendron-FG1-EG2)
Weigh Compound 9 (50mg, 24 μm of ol), compound 4 (204mg, 177 μm of ol), [Pd2 (dba)3]·CHCl3
(5mg,4.8μmol),and HP(tBu)3·BF4Two mouthfuls of round-bottomed flasks of 25mL are added in (4mg, 13.8 μm of ol) under nitrogen atmosphere, to
The THF (10.0mL) of the degassing process of degassing process is added in above-mentioned two-mouth bottle, is then added dropwise again into reaction system
K2CO3Aqueous solution (1M, 1.0mL, 1.0mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.After 24 hours, first
By in solution most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collection organic phase, use anhydrous sodium sulfate
Dry organic phase, filtering, rotary evaporation remove solvent, with silica gel chromatograph post separation small molecular weight impurity, then it is pure with gel chromatographic columns
Change isolated 146mg blue solid (compound 10), yield 75%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=8.92 (d, J=4.08Hz, 4H), 8.89 (d, J=4.12Hz, 2H), 8.87
(d, J=4.16Hz, 2H), δ=7.33 (d, J=5.24Hz, 1H), δ=7.23 (s, 1H), δ=7.22 (s, 1H), 7.13-
7.20(m,12H),7.03-7.12(m,13H),6.70-6.72(m,4H),3.99(br,16H),2.78-2.82(m,8H),
1.94(br,8H),1.65-1.71(m,8H),1.20-1.32(m；280H),0.79-0.92ppm(m,60H).
MALDI-TOF MS:m/z calcd for C292H420N8O8S21:4838.7,found:4838.9(matrix:
DCTB)。
(6) synthesis of compound 12 (G2-Dendrimer-FG1-EG2)
Weigh Compound 7 (100mg, 124 μm of ol), compound 11 (1.35g, 559 μm of ol), [Pd2 (dba)3]·CHCl3
(15mg,14μmol),and HP(tBu)3·BF4Two mouthfuls of round-bottomed flasks of 250mL are added in (9mg, 31 μm of ol) under nitrogen atmosphere, to
The THF (100.0mL) of the degassing process of degassing process is added in above-mentioned two-mouth bottle, is then added dropwise again into reaction system
K2CO3Aqueous solution (1M, 10.0mL, 10.0mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.After 24 hours,
First by solution most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collection organic phase, use anhydrous slufuric acid
Sodium dries organic phase, and filtering, rotary evaporation removes solvent, with silica gel chromatograph post separation small molecular weight impurity, then uses gel chromatographic columns
Purifies and separates obtain 745mg blue solid (compound 12), yield 62%.Its characterize data is as follows:
MALDI-TOF MS:m/z calcd for C584H838N16O16S42:9685.4；found:9684.7(matrix:
DCTB),HR MS:m/z calcd for C584H838N16O16S42: (100%abundance) 9685.3664；Found:
9685.3677.Mn=10463g/mol, Mw=11119, PDI=1.07.
(7) synthesis of compound 15
It weighs (compound 13) (2.0g, 3.32mmol), compound 14 (1.08g, 4.15mmol), Pd2(dba)3.CHCl3
(86mg,83μmol),HP(tBu)3BF4Two mouthfuls of round-bottomed flasks of 500mL, Xiang Shangshu is added in (48mg, 166 μm of ol) under nitrogen atmosphere
The THF (250mL) of the degassing process of degassing process is added in two-mouth bottle, K is then added dropwise into reaction system again2CO3It is water-soluble
Liquid (1M, 15.0mL, 15.0mmol), ambient temperature overnight stirring.Reaction system gradually becomes bluish violet.After 24 hours, first by solution
In most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collect organic phase, with anhydrous sodium sulfate dry have
Machine phase, filtering, rotary evaporation remove solvent, and with silica gel chromatographic column separation product, eluent is methylene chloride: n-hexane (1:3),
Obtain 2.0g blue solid (compound 15), yield 92%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=8.96 (d, 1H), δ=8.88 (d, 1H), 7.79 (m, 2H), 7.67-7.70
(m,2H),7.55(s,1H),7.43(dd,1H),7.36(m,2H),4.03-4.01(m,4H),1.50-1.60(m,2H),
1.21-1.34(m；16H),0.83-0.92ppm(m,12H).
MALDI-TOF MS:m/z calcd for C38H44N2O2S3:656.3,found:656.4(matrix:DCTB)。
(8): the synthesis of compound 16
[Ir (OMe) (COD)] is weighed in glove box2(62mg, 94 μm of ol), HBPin (600mg, 4.68mmol),
Dtbpy (50mg, 186 μm of ol), is sufficiently stirred, is sufficiently mixed three kinds of substances, forms catalyst system.Weigh Compound 15
(2g, 3.05mmol) is added in 100mL two mouth flask, and the dry THF of 50mL is added into the two mouth flask.By catalyst system
It is added in the two mouth flask for filling compound 15, is reacted 4 hours at 50 DEG C.When reaction is cooled to room temperature, solvent is rotated
Obtain crude product.Crude product obtains compound 16 (2.15g), yield 90% by silica gel chromatograph post separation.Its characterize data is such as
Under:
1HNMR(CDCl3, 400MHz): δ=8.95 (d, 1H), 8.86 (d, 1H), 7.79 (d, 1H), 7.65-7.72 (m,
2H),7.52(s,1H),7.40(dd,1H),7.36(m,2H),4.06-4.02(m,4H),1.53-1.63(m,2H),1.24-
1.36(m；16H),1.28(s,12H)0.82-0.93ppm(m,12H).
MALDI-TOF MS:m/z calcd for C44H55BN2O4S3:782.3,found:782.7(matrix:
DCTB)。
(9) synthesis of compound 18
It weighs (compound 17) (200mg, 653 μm of ol), compound 16 (1.29g, 1650 μm of ol), Pd2(dba)3 .CHCl3
(34mg,33μmol),HP(t-Bu)3 .BF4Two mouthfuls of round-bottomed flasks of 100mL, Xiang Shangshu is added in (20mg, 66 μm of ol) under nitrogen atmosphere
The THF (10.0mL) of the degassing process of degassing process is added in two-mouth bottle, K is then added dropwise into reaction system again2CO3Water
Solution (1M, 2.5mL, 2.5mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.After 24 hours, first by solution
In most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collect organic phase, with anhydrous sodium sulfate dry have
Machine phase, filtering, rotary evaporation remove solvent, and with silica gel chromatographic column separation product, eluent is methylene chloride: n-hexane (1:2),
Obtain 810mg blue solid (compound 18), yield 85%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=8.98 (m, 2H), δ=8.90 (m, 2H), 7.85 (m, 3H), 7.80 (m,
2H),7.68-7.74(m,4H),7.55(m,2H),7.42(m,2H),7.36-7.38(m,4H),4.06-4.02(m,8H),
1.53-1.63(m,4H),1.22-1.35(m；32H),0.84-0.95ppm(m,24H),0.29(s,9H).
MALDI-TOF MS:m/z calcd for C85H98N4O4S6Si:1458.6,found:1458.8(matrix:
DCTB)。
(10) synthesis of compound 19
Weigh Compound 18 (1.0g, 685 μm of ol) is dissolved in 100ml CH2Cl2In, it is added dropwise under 0 DEG C of nitrogen atmosphere
BBr3 (1.0Ml, 1M, 1mmol), continues to stir 2h after being added dropwise, and removes easy volatile solvent therein with high-vacuum pump.Claim again
It takes pinacol (97mg, 820 μm of ol) to be dissolved in 100mL THF, dissolved pinacol solution is injected into above-mentioned reactant
In system, ambient temperature overnight stirring.After 24 hours, first most of solvent in solution is concentrated by evaporation, then is extracted with methylene chloride/water
Solution collects organic phase, and with the dry organic phase of anhydrous sodium sulfate, filtering, rotary evaporation removes solvent, with silica gel chromatograph post separation
Product, eluent are methylene chloride: n-hexane (3:7) obtains 912mg blue solid (compound 19), yield 88%.
1H NMR(CDCl3, 400MHz): δ=8.99 (m, 2H), δ=8.92 (m, 2H), 7.86 (m, 3H), 7.82 (m,
2H),7.67-7.75(m,4H),7.54(m,2H),7.45(m,2H),7.33-7.40(m,4H),4.03-4.09(m,8H),
1.54-1.65(m,4H),1.31(s,12H),1.20-1.36(m；32H),0.83-0.94ppm(m,24H).
MALDI-TOF MS:m/z calcd for C88H101BN4O6S6:1512.6,found:1512.9(matrix:
DCTB)。
(11) compound 20 is synthetically prepared
Weigh Compound 13 (100mg, 215 μm of ol), compound 19 (1.5g, 992 μm of ol), [Pd2 (dba)3]·CHCl3
(25mg,24μmol),and HP(tBu)3·BF4Two mouthfuls of round-bottomed flasks of 250mL are added in (15mg, 51 μm of ol) under nitrogen atmosphere,
The THF (100.0mL) of the degassing process of degassing process is added into above-mentioned two-mouth bottle, is then added dropwise again into reaction system
K2CO3Aqueous solution (1M, 10.0mL, 10.0mmol), ambient temperature overnight stirring.After 24 hours, first most of solvent in solution is steamed
Hair concentration, then methylene chloride/water extraction solution is used, organic phase is collected, with the dry organic phase of anhydrous sodium sulfate, filtering, rotation steaming
Hair removes solvent, obtains 850mg blue solid with silica gel chromatograph post separation small molecular weight impurity, then with gel chromatographic columns purifies and separates
(compound 20), yield 70%.Its characterize data is as follows: MALDI-TOF MS:m/z calcd for C340H362N16O16S24:
5692.1,found:5692.5(matrix:DCTB).Mn=6203g/mol, Mw=6513g/mol, PDI=1.05.
(12) synthesis of compound 22
It weighs (compound 21) (200mg, 199 μm of ol), compound 2 (61mg, 207 μm of ol), Pd2(dba)3 .CHCl3
(10mg,10μmol),HP(t-Bu)3 .BF4Two mouthfuls of round-bottomed flasks of 100mL, Xiang Shangshu is added in (6mg, 20 μm of ol) under nitrogen atmosphere
The THF (20.0mL) of the degassing process of degassing process is added in two-mouth bottle, K is then added dropwise into reaction system again2CO3Water
Solution (1M, 2.5mL, 2.5mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.After 24 hours, first by solution
In most of solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collect organic phase, with anhydrous sodium sulfate dry have
Machine phase, filtering, rotary evaporation remove solvent, and with silica gel chromatographic column separation product, eluent is methylene chloride: n-hexane (1:3),
Obtain 87mg blue solid (compound 22), yield 40%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=7.78 (m, 2H), δ=7.69 (m, 2H), 7.52 (m, 2H), 7.40 (m,
2H),7.32(d,1H),6.74(d,1H),3.90-3.95(m,4H),2.81-2.85(m,2H),1.90-1.98(m,2H),
1.66-1.74(m,2H),1.21-1.34(m；70H),0.83-0.92ppm(m,15H).
MALDI-TOF MS:m/z calcd for C68H105BrN2O2S:1092.7,Found:1093.0(matrix:
DCTB)。
(13) synthesis of compound 24
Weigh Compound 23 (100mg, 200 μm of ol), compound 22 (546mg, 500 μm of ol), Pd2(dba)3 .CHCl3
(10mg,10μmol),HP(t-Bu)3 .BF4Two mouthfuls of round-bottomed flasks of 25mL are added in (8mg, 27 μm of ol) under nitrogen atmosphere, to above-mentioned two
The THF (20.0mL) of the degassing process of degassing process is added in mouth bottle, K is then added dropwise into reaction system again2CO3It is water-soluble
Liquid (1M, 2mL, 2mmol), ambient temperature overnight stirring.Reaction system gradually becomes navy blue.It, first will be big in solution after 24 hours
Partial solvent be concentrated by evaporation, then use methylene chloride/water extraction solution, collect organic phase, with anhydrous sodium sulfate dry organic phase, mistake
Filter, rotary evaporation remove solvent, and with silica gel chromatographic column separation product, eluent is methylene chloride: n-hexane (3:7) obtains
372mg blue solid (compound 24), yield 82%.Its characterize data is as follows:
1H NMR(CDCl3, 400MHz): δ=7.80 (m, 4H), δ=7.76 (d, 1H), 7.70 (m, 4H), 7.55 (m,
4H), 7.42 (m, 4H), 7.30-7.35 (m, 4H), 7.20 (d, 1H), 7.16 (d, 2H), 6.76 (d, 2H), 4.02 (d, J=
7.00Hz, 8H), 2.81 (t, J=7.56Hz, 4H), 1.94-1.99 (m, 4H), 1.66-1.73 (m, 4H), 1.21-1.34 (m；
140H),0.81-0.93ppm(m,30H)。
MALDI-TOF MS:m/z calcd for C148H216N4O4S5:2273.5,found:2273.0(matrix:
DCTB)。
(14) synthesis of compound 25
[Ir (OMe) (COD)] is weighed in glove box2(66mg, 100 μm of ol), HBPin (340mg, 2.66mmol),
Dtbpy (54mg, 200 μm of ol), is sufficiently stirred, is sufficiently mixed three kinds of substances, forms catalyst system.Weigh Compound 24
(3g, 1.32mmol) is added in 250mL two mouth flask, and the dry THF of 100mL is added into the two mouth flask.By caltalyst
System is added in the two mouth flask for filling compound 24, reacts 4 hours at 50 DEG C.When reaction is cooled to room temperature, rotate molten
Agent obtains crude product.Crude product obtains compound 25 (2.69g), yield 85% by silica gel chromatograph post separation.
1H NMR(CDCl3, 400MHz): δ=7.84 (m, 4H), 7.60 (s, 1H), 7.73 (m, 4H), 7.57 (m, 4H),
7.45 (m, 4H), 7.32-7.37 (m, 4H), 7.18 (d, 2H), 6.79 (d, 2H), 4.05 (d, J=7.00Hz, 8H), 2.83 (t,
J=7.56Hz, 4H), 1.92-1.98 (m, 4H), 1.64-1.71 (m, 4H), 1.33 (s, 12H), 1.21-1.34 (m；140H),
0.81-0.93ppm(m,30H)。
MALDI-TOF MS:m/z calcd for C148H216N4O4S5:2399.6,found:2400.0(matrix:
DCTB)。
(15) synthesis of compound 26
Weigh Compound 9 (80mg, 64 μm of ol), compound 25 (695mg, 290 μm of ol), [Pd2 (dba)3]·CHCl3
(10mg,10μmol),and HP(tBu)3·BF4Two mouthfuls of round-bottomed flasks of 250mL are added in (6mg, 19 μm of ol) under nitrogen atmosphere,
The THF (120.0mL) of the degassing process of degassing process is added into above-mentioned two-mouth bottle, is then added dropwise again into reaction system
K2CO3Aqueous solution (1M, 3mL, 3.0mmol), ambient temperature overnight stirring.It is first that most of solvent evaporation in solution is dense after 24 hours
Contracting, then methylene chloride/water extraction solution is used, organic phase is collected, with the dry organic phase of anhydrous sodium sulfate, is filtered, rotary evaporation removes
Solvent is removed, with silica gel chromatograph post separation small molecular weight impurity, then 392mg blue solid is obtained with gel chromatographic columns purifies and separates and (changes
Close object 26), yield 62%.Its characterize data is as follows: MALDI-TOF MS:m/z calcd for C628H876N16O16S29:
9826.0,found:9826.8(matrix:DCTB).Mn=8963g/mol, Mw=9680g/mol, PDI=1.08.
(16) synthesis of compound 28
Weigh Compound 13 (50mg, 107 μm of ol), compound 27 (785mg, 483 μm of ol), [Pd2 (dba)3]·CHCl3
(10mg,10μmol),and HP(tBu)3·BF4Two mouthfuls of round-bottomed flasks of 250mL are added in (6mg, 19 μm of ol) under nitrogen atmosphere,
The THF (150.0mL) of the degassing process of degassing process is added into above-mentioned two-mouth bottle, is then added dropwise again into reaction system
K2CO3Aqueous solution (1M, 5mL, 5.0mmol), ambient temperature overnight stirring.It is first that most of solvent evaporation in solution is dense after 24 hours
Contracting, then methylene chloride/water extraction solution is used, organic phase is collected, with the dry organic phase of anhydrous sodium sulfate, is filtered, rotary evaporation removes
Solvent is removed, with silica gel chromatograph post separation small molecular weight impurity, then 428mg blue solid is obtained with gel chromatographic columns purifies and separates and (changes
Close object 28), yield 65%.Its characterize data is as follows: MALDI-TOF MS:m/z calcd for C356H362N16O16S32:
6139.9,found:6139.5(matrix:DCTB).Mn=6954g/mol, Mw=7371g/mol, PDI=1.06.
Embodiment 1: the preparation of three-dimensional tree-like conjugated compound (6T-DPP)-compound ink of carbon nanotube
2mg commercialization Large Diameter Pipeline carbon nanotube P2 sample is weighed, is dissolved in 10 milliliters of toluene solution, molecule is then added
The tree-like conjugated compound 6T-DPP 6mg of three-dimensional that amount is 4597, the supersonic cleaning machine for being 60W with power under conditions of ice bath
It ultrasonic disperse 30 minutes, is sufficiently acted on semiconductor carbon nanometer tube with making the polymer property of can choose, obtains evenly dispersed point
Dispersion liquid.After being centrifuged 30 minutes using 15000rpm, make carbon nano-tube bundle in above-mentioned dispersion liquid and not by three-dimensional tree-like total
The metallic carbon nanotubes of compound conjugate cladding are deposited on the bottom of centrifuge tube, and isolating supernatant liquor can be obtained high-purity richness
Collection has the compound ink of Large Diameter Pipeline semiconductor carbon nanometer tube.
Embodiment 2: the preparation of three-dimensional tree-like conjugated compound (9T-DPP)-compound ink of carbon nanotube
2mg commercialization Large Diameter Pipeline carbon nanotube P2 sample is weighed, is dissolved in 10 milliliters of toluene solution, molecule is then added
The tree-like conjugated compound 9T-DPP 6mg of three-dimensional that amount is 4848, the supersonic cleaning machine for being 60W with power under conditions of ice bath
It ultrasonic disperse 30 minutes, is sufficiently acted on semiconductor carbon nanometer tube with making the polymer property of can choose, obtains evenly dispersed point
Dispersion liquid.After being centrifuged 30 minutes using 15000rpm, make carbon nano-tube bundle in above-mentioned dispersion liquid and not by three-dimensional tree-like total
The metallic carbon nanotubes of compound conjugate cladding are deposited on the bottom of centrifuge tube, and separation supernatant liquor can be obtained high-purity enrichment
There is the compound ink of Large Diameter Pipeline semiconductor carbon nanometer tube.
Embodiment 3: the preparation of three-dimensional tree-like conjugated compound (18T-DPP)-compound ink of carbon nanotube
2mg commercialization Large Diameter Pipeline carbon nanotube P2 sample is weighed, is dissolved in 10 milliliters of toluene solution, molecule is then added
The tree-like conjugated compound 18T-DPP 6mg of three-dimensional that amount is 9846, the supersonic cleaning machine for being 60W with power under conditions of ice bath
It ultrasonic disperse 30 minutes, is sufficiently acted on semiconductor carbon nanometer tube with making the polymer property of can choose, obtains evenly dispersed point
Dispersion liquid.After being centrifuged 30 minutes using 15000rpm, make carbon nano-tube bundle in above-mentioned dispersion liquid and not by three-dimensional tree-like total
The metallic carbon nanotubes of compound conjugate cladding are deposited on the bottom of centrifuge tube, and separation supernatant liquor can be obtained high-purity enrichment
There is the compound ink of Large Diameter Pipeline semiconductor carbon nanometer tube.
Embodiment 4: the UV-Vis-IR spectrum of three-dimensional tree-like conjugated compound (6T-DPP)-compound ink of carbon nanotube
It can characterization
To the supernatant after three-dimensional tree-like conjugated compound (6T-DPP)-carbon nano tube dispersion liquid centrifugation, using it is ultraviolet-can
See-near-infrared (Perkin Elmer Lambda 750) tests its absorption spectrum, result is as shown in Figure 1.From abosrption spectrogram
In as can be seen that the S22 absorption peak (900-1200nm) of corresponding semiconductor carbon nanometer tube becomes very sharp, and absorb background
It is very low, illustrate the dispersion enriched semiconductor carbon nanotube of three-dimensional tree-like conjugated compound (6T-DPP) property of can choose.
Embodiment 5: the UV-Vis-IR spectrum of three-dimensional tree-like conjugated compound (9T-DPP)-compound ink of carbon nanotube
It can characterization
To the supernatant after three-dimensional tree-like conjugated compound (9T-DPP)-carbon nano tube dispersion liquid centrifugation, using it is ultraviolet-can
See-near-infrared (Perkin Elmer Lambda 750) tests its absorption spectrum, result is as shown in Figure 2.From abosrption spectrogram
In as can be seen that the S22 absorption peak (900-1200nm) of corresponding semiconductor carbon nanometer tube becomes very sharp, and absorb background
It is very low, illustrate the dispersion enriched semiconductor carbon nanotube of three-dimensional tree-like conjugated compound (9T-DPP) property of can choose.
Embodiment 6: the Raman spectrum property table of three-dimensional tree-like conjugated compound (6T-DPP)-compound ink of carbon nanotube
Sign
The Raman spectrum of the supernatant after above-mentioned centrifugation is tested using Raman spectrometer.Its Raman spectrum is illustrated in Fig. 3
Test result.Under the laser of 785nm, in untreated carbon nanotube P2 it can be observed that and 159cm-1Metallicity carbon is received
The corresponding peak of mitron, but pass through the selective coated of three-dimensional tree-like conjugated compound (6T-DPP) and be centrifugally separating to obtain
In sample, 159cm-1Metallic carbon nanotubes peak disappears.Therefore, it can be assumed that, according to the embodiment of the present invention 1 method can efficiently
Isolate the semiconductor carbon nanometer tube of a large amount of Large Diameter Pipelines in ground.
Embodiment 7: the Raman spectrum property table of three-dimensional tree-like conjugated compound (9T-DPP)-compound ink of carbon nanotube
Sign
The Raman spectrum of the supernatant after above-mentioned centrifugation is tested using Raman spectrometer.It has been represented in Fig. 4 its Raman spectrum
Test result.Under the laser of 633nm, for being observed that and metallic carbon nanotubes phase in untreated carbon nanotube P2
Corresponding peak (1550-1580cm-1) and peak (1590cm corresponding with semiconductor carbon nanometer tube-1), but pass through three-dimensional tree-like
It the selective coated of conjugated compound (9T-DPP) and is centrifugally separating to obtain in sample, 1590cm-1The semiconductor carbon nanometer at place
Guan Feng becomes more sharp, while compared with unsegregated P2 carbon nanotube, the corresponding peak semiconductor of metallic carbon nanotubes
The ratio between the peak area at carbon nanotube peak becomes smaller.It therefore, it can be shown that can be efficiently according to the method for the embodiment of the present invention 2
Isolate the semiconductor carbon nanometer tube of a large amount of Large Diameter Pipelines.
Embodiment 8: the thin film transistor (TFT) preparation of three-dimensional tree-like conjugated compound (9T-DPP)-compound ink of carbon nanotube with
And performance characterization
Take the Large Diameter Pipeline isolated in above-described embodiment 2 using three-dimensional tree-like conjugated compound (9T-DPP) selective coated
The ink solution of P2 semiconductor carbon nanometer tube prepares film transistor device with the method that drop coating is processed.Fig. 5 is the electricity of transistor
Performance transfer characteristic curve, it can be seen from the figure that the on-off ratio of transistor and mobility can achieve 4 × 10 respectively6With
37.63cm2/ Vs or more.Fig. 6 is the output indicatrix of the electrical property of transistor, it can be seen from the figure that the transistor exports
Electric current increases with gate voltage and is become smaller, which is p-type transistor.There is the transistor excellent electrical property further to confirm
By the selective coated of three-dimensional tree-like conjugated compound, can be very good to carry out separation commercialization Large Diameter Pipeline carbon nanotube.
In addition, referring to the embodiment of embodiment 1-8, inventor also with the compound 20,26 listed above and its
Its compound is tested, and has obtained similar test result.
It should be appreciated that it is described above and shown in embodiment, the design philosophy surely of the invention that is limited can not be parsed.In this hair
Technical staff in bright technical field can by technical thought of the invention according to the prior art and the common sense of this field with
Various form improves change, and such improvement and change are interpreted as belonging to the scope of protection of the present invention interior.
Claims (117)
1. purposes of the three-dimensional tree-like conjugated compound in Selective Separation semiconductor type carbon nano-tube, the tree-like conjugation of three-dimensional
Compound has structure shown in formula (I) or (II):
Wherein, B is that branching is conjugated link unit, selected from being formed by five yuan or hexa-atomic aromatic units, with branched structure
Unit；
FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):
M is the degree of branching that the branching is conjugated link unit B, and is selected from 2 or 3,
N is repetitive unit the number of iterations in the molecule of the tree-like conjugated compound of three-dimensional, and is selected from 1,2,3 or 4.
2. purposes as described in claim 1, which is characterized in that the end group functionalized modification unit F G includes following formula (III-1),
(III-2) and any one structure shown in (III-3):
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
3. purposes as described in claim 1, which is characterized in that further include leading-in end position in the end group functionalized modification unit F G
Blocking units, the blocking units include following formula (EG-1), any one structure shown in (EG-2) and (EG-3):
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
4. purposes as described in claim 1, which is characterized in that the end group functionalized modification unit F G has following any
Structure:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
5. purposes as described in claim 1, which is characterized in that branching conjugation link unit B include following formula (IV-1),
(IV-2), any one structure shown in (IV-3) and (IV-4):
Wherein, Y includes phenyl ring and/or thiophene unit, and D includes phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units shape
At condensed ring unit or the conjugation short chain units that are formed by 2~4 five yuan or hexa-atomic aromatic units.
6. purposes as claimed in claim 5, which is characterized in that branching conjugation link unit B has following any
Structure:
7. purposes as described in claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Structure:
8. purposes as described in claim 1, which is characterized in that branching conjugation link unit B has following any
Structure:
9. purposes as described in claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Structure:
10. purposes as described in claim 1, which is characterized in that branching conjugation link unit B has following any
Structure:
11. purposes as described in claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Kind structure:
12. purposes as claimed in claim 5, which is characterized in that D has following any structure:
Wherein, X1=S or O, X2The miscellaneous alkyl of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20,
R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
13. purposes as claimed in claim 12, which is characterized in that D has following any structure:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkyl of C1~C20.
14. purposes as described in claim 1, which is characterized in that the branching conjugation link unit B has the following structure:
Wherein, outer end thiophene alpha-position p-a and/or p-b is connected with end group functionalized modification unit F G, or with inner end thiophene alpha-position c-
A, which is connected to form, is conjugated link unit with high algebra branching shown in following formula (V-G2), (V-G3) or (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with end group functionalized modification unit F G, and the thiophene alpha-position of kernel is that hydrogen is former
The molecule with structure shown in (II) is connected to form between the thiophene alpha-position of son or two kernels.
15. purposes as described in claim 1, which is characterized in that the branching conjugation link unit B has knot shown in following formula
Structure:
16. purposes as described in claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Kind structure:
17. purposes of the three-dimensional tree-like conjugated compound as Carbon nano-tube dispersant, the tree-like conjugated compound of three-dimensional have
Structure shown in formula (I) or (II):
Wherein, B is that branching is conjugated link unit, selected from being formed by five yuan or hexa-atomic aromatic units, with branched structure
Unit；
FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):
M is the degree of branching that the branching is conjugated link unit B, and is selected from 2 or 3,
N is repetitive unit the number of iterations in the molecule of the tree-like conjugated compound of three-dimensional, and is selected from 1,2,3 or 4；
The carbon nanotube is semiconductor type carbon nano-tube.
18. purposes as claimed in claim 17, which is characterized in that the end group functionalized modification unit F G includes following formula (III-
1), any one structure shown in (III-2) and (III-3):
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
19. purposes as claimed in claim 18, which is characterized in that further include leading-in end in the end group functionalized modification unit F G
The blocking units of position, the blocking units include following formula (EG-1), any one structure shown in (EG-2) and (EG-3):
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
20. purposes as claimed in claim 17, which is characterized in that the end group functionalized modification unit F G has following any
Kind structure:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
21. purposes as claimed in claim 17, which is characterized in that branching conjugation link unit B include following formula (IV-1),
(IV-2), any one structure shown in (IV-3) and (IV-4):
Wherein, Y includes phenyl ring and/or thiophene unit, and D includes phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units shape
At condensed ring unit or the conjugation short chain units that are formed by 2~4 five yuan or hexa-atomic aromatic units.
22. purposes as claimed in claim 21, which is characterized in that the branching conjugation link unit B has following any
Kind structure:
23. purposes as claimed in claim 17, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Kind structure:
24. purposes as claimed in claim 17, which is characterized in that the branching conjugation link unit B has following any
Kind structure:
25. purposes as claimed in claim 17, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Kind structure:
26. purposes as claimed in claim 17, which is characterized in that the branching conjugation link unit B has following any
Kind structure:
27. purposes as claimed in claim 17, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Kind structure:
28. purposes as claimed in claim 21, which is characterized in that D has following any structure:
Wherein, X1=S or O, X2The miscellaneous alkyl of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20,
R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
29. purposes as claimed in claim 28, which is characterized in that D has following any structure:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkyl of C1~C20.
30. purposes as claimed in claim 17, which is characterized in that the branching conjugation link unit B has the following structure:
Wherein, outer end thiophene alpha-position p-a and/or p-b is connected with end group functionalized modification unit F G, or with inner end thiophene alpha-position c-
A, which is connected to form, is conjugated link unit with high algebra branching shown in following formula (V-G2), (V-G3) or (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with end group functionalized modification unit F G, and the thiophene alpha-position of kernel is that hydrogen is former
The molecule with structure shown in (II) is connected to form between the thiophene alpha-position of son or two kernels.
31. purposes as claimed in claim 17, which is characterized in that the branching conjugation link unit B has knot shown in following formula
Structure:
32. purposes as claimed in claim 17, which is characterized in that the tree-like conjugated compound of three-dimensional has following any
Kind structure:
33. a kind of tree-like conjugated compound-carbon mano-tube composite of three-dimensional, characterized by comprising:
Carbon nanotube,
And at least it is attached to the tree-like conjugated compound of three-dimensional in the part of the surface of carbon nanotube；
Wherein, the tree-like conjugated compound of three-dimensional has structure shown in formula (I) or (II):
Wherein, B is that branching is conjugated link unit, selected from being formed by five yuan or hexa-atomic aromatic units, with branched structure
Unit,
FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):
M is the degree of branching that the branching is conjugated link unit B, and is selected from 2 or 3,
N is repetitive unit the number of iterations in the molecule of the tree-like conjugated compound of three-dimensional, and is selected from 1,2,3 or 4；
The carbon nanotube is semiconductor type carbon nano-tube.
34. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the end
Base functionalized modification unit F G includes following formula (III-1), any one structure shown in (III-2) and (III-3):
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
35. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the end
It further include the blocking units of leading-in end position in base functionalized modification unit F G, the blocking units include following formula (EG-1), (EG-2)
Any one structure shown in (EG-3):
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
36. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the end
Base functionalized modification unit F G has following any structure:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
37. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the branch
Changing conjugation link unit B includes following formula (IV-1), (IV-2), any one structure shown in (IV-3) and (IV-4):
Wherein, Y includes phenyl ring and/or thiophene unit, and D includes phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units shape
At condensed ring unit or the conjugation short chain units that are formed by 2~4 five yuan or hexa-atomic aromatic units.
38. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the branch
Changing conjugation link unit B has following any structure:
39. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that described three
Tree-like conjugated compound is tieed up with following any structure:
40. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the branch
Changing conjugation link unit B has following any structure:
41. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that described three
Tree-like conjugated compound is tieed up with following any structure:
42. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the branch
Changing conjugation link unit B has following any structure:
43. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that described three
Tree-like conjugated compound is tieed up with following any structure:
44. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 37, which is characterized in that under D has
Any structure of column:
Wherein, X1=S or O, X2The miscellaneous alkyl of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20,
R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
45. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 44, which is characterized in that under D has
Any structure of column:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkyl of C1~C20.
46. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the branch
Change conjugation link unit B to have the following structure:
Wherein, outer end thiophene alpha-position p-a and/or p-b is connected with end group functionalized modification unit F G, or with inner end thiophene alpha-position c-
A, which is connected to form, is conjugated link unit with high algebra branching shown in following formula (V-G2), (V-G3) or (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with end group functionalized modification unit F G, and the thiophene alpha-position of kernel is that hydrogen is former
The molecule with structure shown in (II) is connected to form between the thiophene alpha-position of son or two kernels.
47. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that the branch
Changing conjugation link unit B has structure shown in following formula:
48. three-dimensional tree-like conjugated compound-carbon mano-tube composite as claimed in claim 33, which is characterized in that described three
Tree-like conjugated compound is tieed up with following any structure:
49. a kind of carbon nano tube dispersion method, characterized by comprising: take three-dimensional tree-like conjugated compound and carbon nanotube in molten
It is uniformly mixed in agent, forms the carbon nano tube dispersion liquid of stable and uniform；
Wherein, the tree-like conjugated compound of three-dimensional has structure shown in formula (I) or (II):
Wherein, B is that branching is conjugated link unit, selected from being formed by five yuan or hexa-atomic aromatic units, with branched structure
Unit,
FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):
M is the degree of branching that the branching is conjugated link unit B, and is selected from 2 or 3,
N is repetitive unit the number of iterations in the molecule of the tree-like conjugated compound of three-dimensional, and is selected from 1,2,3 or 4；
The carbon nanotube is semiconductor type carbon nano-tube.
50. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the end group functionalized modification unit F G packet
It includes following formula (III-1), any one structure shown in (III-2) and (III-3):
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
51. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that in the end group functionalized modification unit F G
It further include the blocking units of leading-in end position, the blocking units include following formula (EG-1), any shown in (EG-2) and (EG-3)
A kind of structure:
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
52. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the end group functionalized modification unit F G tool
There is following any structure:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
53. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the branching is conjugated link unit B packet
Following formula (IV-1), (IV-2) are included, any one structure shown in (IV-3) and (IV-4):
Wherein, Y includes phenyl ring and/or thiophene unit, and D includes phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units shape
At condensed ring unit or the conjugation short chain units that are formed by 2~4 five yuan or hexa-atomic aromatic units.
54. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the branching conjugation link unit B tool
There is following any structure:
55. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the tree-like conjugated compound tool of three-dimensional
There is following any structure:
56. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the branching conjugation link unit B tool
There is following any structure:
57. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the tree-like conjugated compound tool of three-dimensional
There is following any structure:
58. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the branching conjugation link unit B tool
There is following any structure:
59. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the tree-like conjugated compound tool of three-dimensional
There is following any structure:
60. carbon nano tube dispersion method as claimed in claim 53, which is characterized in that D has following any structure:
Wherein, X1=S or O, X2The miscellaneous alkyl of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20,
R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
61. carbon nano tube dispersion method as claimed in claim 60, which is characterized in that D has following any structure:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkyl of C1~C20.
62. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the branching conjugation link unit B tool
Just like flowering structure:
Wherein, outer end thiophene alpha-position p-a and/or p-b is connected with end group functionalized modification unit F G, or with inner end thiophene alpha-position c-
A, which is connected to form, is conjugated link unit with high algebra branching shown in following formula (V-G2), (V-G3) or (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with end group functionalized modification unit F G, and the thiophene alpha-position of kernel is that hydrogen is former
The molecule with structure shown in (II) is connected to form between the thiophene alpha-position of son or two kernels.
63. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the branching conjugation link unit B tool
There is structure shown in following formula:
64. carbon nano tube dispersion method as claimed in claim 49, which is characterized in that the tree-like conjugated compound tool of three-dimensional
There is following any structure:
65. a kind of method of Selective Separation semiconductor type carbon nano-tube, characterized by comprising:
Carbon nanotube dust is added in the solution of three-dimensional tree-like conjugated compound and is sufficiently mixed, semi-conductor type carbon therein is made
Nanotube is dispersed in solution,
And remove the carbon nanotube for failing to be scattered in solution；
Wherein, the tree-like conjugated compound of three-dimensional has structure shown in formula (I) or (II):
Wherein, B is that branching is conjugated link unit, selected from being formed by five yuan or hexa-atomic aromatic units, with branched structure
Unit,
FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):
M is the degree of branching that the branching is conjugated link unit B, and is selected from 2 or 3,
N is repetitive unit the number of iterations in the molecule of the tree-like conjugated compound of three-dimensional, and is selected from 1,2,3 or 4.
66. separation method according to claim 65, it is characterised in that: the end group functionalized modification unit F G includes following formula
(III-1), any one structure shown in (III-2) and (III-3):
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
67. the separation method as described in claim 65, which is characterized in that further include drawing in the end group functionalized modification unit F G
Enter to hold the blocking units of position, the blocking units include following formula (EG-1), any one structure shown in (EG-2) and (EG-3):
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
68. the separation method as described in claim 65, which is characterized in that the end group functionalized modification unit F G has following
Any structure:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
69. the separation method as described in claim 65, which is characterized in that the branching conjugation link unit B includes following formula
(IV-1), (IV-2), any one structure shown in (IV-3) and (IV-4):
Wherein, Y includes phenyl ring and/or thiophene unit, and D includes phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units shape
At condensed ring unit or the conjugation short chain units that are formed by 2~4 five yuan or hexa-atomic aromatic units.
70. the separation method as described in claim 69, which is characterized in that the branching conjugation link unit B has following
Any structure:
71. the separation method as described in claim 65, which is characterized in that the tree-like conjugated compound of three-dimensional has following
Any structure:
72. the separation method as described in claim 65, which is characterized in that the branching conjugation link unit B has following
Any structure:
73. the separation method as described in claim 65, which is characterized in that the tree-like conjugated compound of three-dimensional has following
Any structure:
74. the separation method as described in claim 65, which is characterized in that the branching conjugation link unit B has following
Any structure:
75. the separation method as described in claim 65, which is characterized in that the tree-like conjugated compound of three-dimensional has following
Any structure:
76. the separation method as described in claim 69, which is characterized in that D has following any structure:
Wherein, X1=S or O, X2The miscellaneous alkyl of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20,
R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
77. the separation method as described in claim 76, which is characterized in that D has following any structure:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkyl of C1~C20.
78. the separation method as described in claim 65, which is characterized in that the branching conjugation link unit B has following knot
Structure:
Wherein, outer end thiophene alpha-position p-a and/or p-b is connected with end group functionalized modification unit F G, or with inner end thiophene alpha-position c-
A, which is connected to form, is conjugated link unit with high algebra branching shown in following formula (V-G2), (V-G3) or (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with end group functionalized modification unit F G, and the thiophene alpha-position of kernel is that hydrogen is former
The molecule with structure shown in (II) is connected to form between the thiophene alpha-position of son or two kernels.
79. the separation method as described in claim 65, which is characterized in that the branching conjugation link unit B has following formula institute
Show structure:
80. the separation method as described in claim 65, which is characterized in that the tree-like conjugated compound of three-dimensional has following
Any structure:
81. including the carbon of the tree-like conjugated compound-carbon mano-tube composite of three-dimensional described in any one of claim 33-48
Nanotube dispersion.
82. a kind of compound ink, characterized by comprising:
Tree-like conjugated compound-the carbon mano-tube composite of three-dimensional described in any one of claim 33-48,
And at least one solvent, disperse to cooperatively form stable homogeneous liquid phase with remaining component of the compound ink
System.
83. the compound ink according to claim 82, it is characterised in that: the solvent includes that can dissolve the three-dimensional tree
The organic solvent of shape conjugated compound.
84. the compound ink according to claim 83, it is characterised in that: the organic solvent includes chloroform, tetrahydro
Furans, toluene, ortho-xylene, paraxylene, any one or two or more combinations in meta-xylene.
85. the compound ink according to claim 82, it is characterised in that: the compound ink also includes except the three-dimensional tree
Organic semiconductor other than shape conjugated compound.
86. the compound ink according to claim 82, it is characterised in that: the compound ink includes 0.0001~1mg/mL
Carbon nanotube.
87. the compound ink according to claim 82, it is characterised in that: the compound ink include concentration be 0.01~
Tree-like conjugated compound-the carbon mano-tube composite of the three-dimensional of 20mg/mL.
88. a kind of method for preparing compound ink described in any one of claim 82-87, characterized by comprising:
The tree-like conjugated compound of three-dimensional and carbon nanotube are uniformly mixed in solvent, form uniform carbon nanotubes dispersion
Liquid, and, high speed centrifugation processing is carried out to the uniform carbon nanotubes dispersion liquid, obtained clear liquid is the compound ink；
The carbon nanotube includes semiconductor type carbon nano-tube.
89. the preparation method as described in claim 88, it is characterised in that: the centrifugal speed of the high speed centrifugation processing is greater than
8000rpm, centrifugation time is in 20min or more.
90. the preparation method as described in claim 89, it is characterised in that: the centrifugal speed of high speed centrifugation processing is
10000~30000rpm, centrifugation time are 30~100min.
91. the preparation method as described in claim 88, it is characterised in that: the tree-like conjugated compound of the three-dimensional and carbon nanotube
Mass ratio be 1:0.1~1:10.
92. the preparation method as described in claim 91, it is characterised in that: the tree-like conjugated compound of the three-dimensional and carbon nanotube
Mass ratio be 1:0.2~1:5.
93. the preparation method as described in claim 88, characterized by comprising: under conditions of temperature≤0 DEG C, by three-dimensional tree
Shape conjugated compound and carbon nanotube uniformly mix in solvent and form uniform carbon nanotubes dispersion liquid.
94. a kind of film, it is characterised in that include the tree-like conjugated compound-of three-dimensional described in any one of claim 33-48
Carbon mano-tube composite.
95. a kind of preparation method of film, characterized by comprising: at least select printing and/or coating method by claim
Compound ink described in any one of nanotube dispersion described in 81 or claim 82-87 is applied in substrate, is formed
The film；
The coating and/or mode of printing include spin-coating, blade coating, slot coated, ink jet printing, silk-screen printing, recessed
Version printing, flexographic printing, any one or two or more combinations in soft impact transfer printing mode.
96. the preparation method according to claim 95, it is characterised in that further include film post-processing step, after the film
Processing step includes cleaning and annealing operation.
97. the preparation method according to claim 96, it is characterised in that: the annealing temperature that the annealing operation uses exists
200 DEG C hereinafter, annealing time is 30~120min.
98. the preparation method according to claim 97, it is characterised in that: the annealing temperature that the annealing operation uses is 25
~120 DEG C, annealing time is 30~60min.
99. a kind of device, it is characterised in that include the tree-like conjugated compound-of three-dimensional described in any one of claim 33-48
Film described in carbon mano-tube composite or claim 94.
100. the device as described in claim 99, it is characterised in that: described device is selected from semiconductor device.
101. the device as described in claim 100, it is characterised in that: described device is field effect transistor, the field-effect
The active layer of transistor includes the three-dimensional tree-like conjugated compound-carbon mano-tube composite or the film.
102. Carbon nano-tube dispersant, it is characterised in that including the tree-like conjugation of three-dimensional with structure shown in formula (I) or (II)
Object is closed,
Wherein, B is that branching is conjugated link unit, selected from being formed by five yuan or hexa-atomic aromatic units, with branched structure
Unit,
FG is end group functionalized modification unit, and it includes pyrrolo-pyrrole-dione units shown in formula (III):
M is the degree of branching that the branching is conjugated link unit B, and is selected from 2 or 3,
N is repetitive unit the number of iterations in the molecule of the tree-like conjugated compound of three-dimensional, and is selected from 1,2,3 or 4；
The carbon nanotube is selected from semiconductor type carbon nano-tube.
103. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the end group functionalized modification unit F G
Including following formula (III-1), any one structure shown in (III-2) and (III-3):
Wherein, R1The miscellaneous alkyl of alkyl or C1~C20 selected from hydrogen atom or substituted or unsubstituted C1~C20.
104. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the end group functionalized modification unit F G
It inside further include the blocking units of leading-in end position, the blocking units include following formula (EG-1), are appointed shown in (EG-2) and (EG-3)
It anticipates a kind of structure:
Wherein, R2The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
105. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the end group functionalized modification unit F G
With following any structure:
Wherein R1, R2For the linear or branched alkyl group of C1~C20 or the miscellaneous alkyl of C1~C20.
106. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the branching is conjugated link unit B
Including following formula (IV-1), (IV-2), any one structure shown in (IV-3) and (IV-4):
Wherein, Y includes phenyl ring and/or thiophene unit, and D includes phenyl ring, thiphene ring, by 2~5 five yuan or hexa-atomic aromatic units shape
At condensed ring unit or the conjugation short chain units that are formed by 2~4 five yuan or hexa-atomic aromatic units.
107. Carbon nano-tube dispersant described in 06 according to claim 1, which is characterized in that the branching is conjugated link unit B
With following any structure:
108. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional
With following any structure:
109. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the branching is conjugated link unit B
With following any structure:
110. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional
With following any structure:
111. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the branching is conjugated link unit B
With following any structure:
112. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional
With following any structure:
113. Carbon nano-tube dispersant described in 06 according to claim 1, which is characterized in that it is characterized in that, D is with following
Any structure:
Wherein, X1=S or O, X2The miscellaneous alkyl of the alkyl or C1~C20 of=O, S, C, N, Si or Se and its attached C1~C20,
R3The miscellaneous alkyl of alkyl or C1~C20 selected from substituted or unsubstituted C1~C20.
114. Carbon nano-tube dispersant described in 13 according to claim 1, which is characterized in that D has following any structure:
Wherein, R4, R5Independently selected from hydrogen atom, the alkyl of substituted or unsubstituted C1~C20 or the miscellaneous alkyl of C1~C20.
115. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the branching is conjugated link unit B
It has the following structure:
Wherein, outer end thiophene alpha-position p-a and/or p-b is connected with end group functionalized modification unit F G, or with inner end thiophene alpha-position c-
A, which is connected to form, is conjugated link unit with high algebra branching shown in following formula (V-G2), (V-G3) or (V-G4):
Wherein the alpha-position of peripheral thiophene unit is connected with end group functionalized modification unit F G, and the thiophene alpha-position of kernel is that hydrogen is former
The molecule with structure shown in (II) is connected to form between the thiophene alpha-position of son or two kernels.
116. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the branching is conjugated link unit B
With structure shown in following formula:
117. Carbon nano-tube dispersant described in 02 according to claim 1, which is characterized in that the tree-like conjugated compound of three-dimensional
With following any structure:
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