CN114672001A - Organic soluble high-conductivity multi-arm thiophene polymer and preparation method and application thereof - Google Patents
Organic soluble high-conductivity multi-arm thiophene polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN114672001A CN114672001A CN202011552215.6A CN202011552215A CN114672001A CN 114672001 A CN114672001 A CN 114672001A CN 202011552215 A CN202011552215 A CN 202011552215A CN 114672001 A CN114672001 A CN 114672001A
- Authority
- CN
- China
- Prior art keywords
- product
- mixed solution
- thiophene
- arm
- dichloromethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 229930192474 thiophene Natural products 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 108
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 74
- 239000011259 mixed solution Substances 0.000 claims description 64
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000706 filtrate Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 6
- 150000003577 thiophenes Chemical class 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000002274 desiccant Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- -1 potassium alkoxide Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- WNOOCRQGKGWSJE-UHFFFAOYSA-N 3,4-dihydro-2h-thieno[3,4-b][1,4]dioxepine Chemical compound O1CCCOC2=CSC=C21 WNOOCRQGKGWSJE-UHFFFAOYSA-N 0.000 claims description 2
- LSPHULWDVZXLIL-UHFFFAOYSA-N Camphoric acid Natural products CC1(C)C(C(O)=O)CCC1(C)C(O)=O LSPHULWDVZXLIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- LSPHULWDVZXLIL-QUBYGPBYSA-N camphoric acid Chemical compound CC1(C)[C@H](C(O)=O)CC[C@]1(C)C(O)=O LSPHULWDVZXLIL-QUBYGPBYSA-N 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 12
- 229960001701 chloroform Drugs 0.000 abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000123 polythiophene Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FGPZBVIFLOFHFM-UHFFFAOYSA-N dodecyl benzenesulfonate;iron Chemical compound [Fe].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 FGPZBVIFLOFHFM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
- C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/514—Electron transport
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses an organic soluble high-conductivity multi-arm thiophene polymer, and a preparation method and application thereof, and belongs to the technical field of preparation of thiophene conductive high-molecular polymers and novel high-molecular functional materials. The polymer designed by the invention has unique structure and mild reaction conditions. By controlling the type and dosage of the oxidant, the obtained polymer chain (in organic solutions such as dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), Tetrahydrofuran (THF), Trichloromethane (TCM), Dichloromethane (DCM) and the like has excellent solubility and higher conductivity.
Description
Technical Field
The invention belongs to the technical field of preparation of thiophene conductive high polymer and novel high polymer functional materials, and particularly relates to an organic soluble high-conductivity multi-arm thiophene polymer and a preparation method and application thereof.
Background
The polymer conductive polymer has attracted public attention in recent years, and has the characteristics of a conductor, such as folding property, high flexibility, large elasticity, strong plasticity and the like, and has the property of a conductor because the polymer conductive polymer has a high conjugated structure to enable electrons to be transmitted in molecules and between molecules. At present, polyaniline, polyacetylene, polypyrrole, polythiophene and the like are commonly used as organic high polymer materials. Among them, polythiophene is a most widely studied and applied polymer conductive material because of its advantages of high conductivity, easy oxidation and synthesis, and stable chemical properties. The material is widely applied to the fields of organic solar cells, antistatic coatings, supercapacitors, flexible display screens, intelligent windows, field emission transistors and the like, has huge development space, and is a star material which is widely concerned in the scientific and technological industry in recent years.
However, the high conjugated structure increases the rigidity of the molecular chain, and the refractory property is not favorable for processing, so that the application of the high conjugated structure in various scenes is limited. Most of the polythiophene aqueous dispersion systems are applied in the current market, and the existence of moisture in electronic devices can corrode the components, shorten the service life of the components and bring great potential safety hazard to the operation of the components. Therefore, an organic dispersible thiophene polymer becomes a hot content of research and development in recent years, and has wide application and development potential.
At present, in order to realize the dispersion of thiophene polymers in an organic system, side chain engineering is mostly adopted to introduce soluble alkyl groups or alkoxy groups and the like into thiophene rings or epoxy rings, and the defects of complex preparation process, strict requirements on reaction conditions, low conductivity, low solubility and the like exist, and a certain gap still exists for the large-scale application of the thiophene polymers.
Disclosure of Invention
The invention aims to provide a preparation method of an organic soluble high-conductivity multi-arm thiophene polymer, aiming at the defects of insolubility, refractoriness, complex preparation process, harsh reaction conditions and the like of the thiophene polymer.
The invention also aims to provide the organic soluble high-conductivity multi-arm thiophene polymer prepared by the preparation method. The thiophene polymer prepared by the method has higher solubility and good stability in an organic solution, and keeps higher conductivity.
It is still another object of the present invention to provide the use of the above-mentioned organic soluble highly conductive multi-arm thiophene polymer.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an organic soluble high-conductivity multi-arm thiophene polymer comprises the following steps:
(1) dissolving vinyl triethoxysilane in a mixed solution of dichloromethane and isopropanol to obtain a mixed solution 1; dissolving potassium alcoholate in a mixed solution of dichloromethane and isopropanol to obtain a mixed solution 2; adding water into the mixed solution 2, stirring, slowly adding the mixed solution 1 into the added water to obtain a mixed solution 2, magnetically stirring, and reacting to obtain a product 1;
(2) adding protonic acid into the product 1, adjusting the pH value to acidity, and continuing to magnetically stir in a nitrogen environment for reaction to obtain a product 2;
(3) filtering the product 2, adding a saturated sodium bicarbonate solution into the filtrate of the product 2 to adjust the pH value to be neutral, and adding an excessive drying agent to remove water; filtering to obtain filtrate, performing rotary evaporation, and performing vacuum drying to obtain a product 3 (tetravinyl silsesquioxane);
(4) adding the product 3, a palladium catalyst, alkali and bromothiophene into N, N-dimethylformamide respectively, and reacting in an argon atmosphere to obtain a product 4 (tetrathiophene-vinyl silsesquioxane);
(5) filtering the product 4, taking the filtrate of the product 4, adding N-acetyl-L-cysteine, stirring, filtering to obtain the filtrate, removing the solvent, and drying to obtain a product 5;
(6) adding cyclohexane into the product 5 to obtain a mixed solution 1; adding a thiophene derivative and an oxidant into acetonitrile to obtain a mixed solution 2; and slowly adding the mixed solution 2 into the mixed solution 1, and reacting to obtain the organic soluble high-conductivity multi-arm thiophene polymer.
The potassium alkoxide described in the step (1) preferably includes at least one of potassium tert-butoxide and potassium methoxide.
In the mixed solution of dichloromethane and isopropanol described in step (1), dichloromethane and isopropanol are preferably calculated in a volume ratio of 1: 1.
The vinyltriethoxysilane and potassium alkoxide described in step (1) are preferably calculated in a molar ratio of 1: 1.
The ratio of water to the mixed solution 2 in the step (1) is preferably calculated in a mass (g) to volume (mL) ratio of 2: 180.
The reaction time in the step (1) is preferably 12-48 h; more preferably 24-48 h.
The protonic acid in the step (2) is preferably hydrochloric acid; more preferably concentrated hydrochloric acid at a concentration of 36%.
The acidity in the step (2) is pH 3-5.
The reaction time in the step (2) is preferably 24-48 h at room temperature; more preferably, the reaction is carried out for 24-48 h at 25-35 ℃.
The drying agent in the step (3) is preferably anhydrous magnesium sulfate.
The rotary evaporation temperature in the step (3) is preferably 50-70 ℃.
The temperature of the vacuum drying in the step (3) is preferably 50-70 ℃, and the time is 12-48 h; more preferably 60 ℃ for 24 hours.
The product 3, the palladium catalyst, the base and the bromothiophene described in step (4) are preferably calculated in a molar ratio of 2:1.28:3: 8.
The palladium catalyst described in step (4) is preferably palladium on carbon.
The base in step (4) is preferably N, N dicyclohexylmethylamine.
The bromothiophene in the step (4) is preferably at least one of 2-bromothiophene and 3-bromothiophene.
The reaction in the step (4) is preferably carried out at 100 ℃ for 24-48 h.
The mass (g) to volume (mL) ratio of the N-acetyl-L-cysteine to the filtrate of the product 4 in the step (5) is preferably 0.05-0.1: 1.
The stirring in the step (5) is preferably performed at room temperature for 12-24 hours; more preferably, the stirring is carried out for 12 to 24 hours at a temperature of between 25 and 35 ℃.
The ratio of the product 5 and cyclohexane in the step (6) is preferably 0.05-0.2: 1 according to a mol (mmol) to volume (mL).
The cyclohexane and the acetonitrile in the step (6) are preferably calculated according to the volume ratio of 1: 1.
The thiophene derivative described in step (6) preferably includes, but is not limited to, at least one of thiophene, 3, 4-ethylenedioxythiophene, and 3, 4-propylenedioxythiophene.
The product 5 and the thiophene derivative in the step (6) are preferably calculated according to a molar ratio of 1: 8-20.
The oxidizing agent in step (6) preferably includes, but is not limited to, at least one of iron trichloride, iron dodecylbenzenesulfonate, iron p-toluenesulfonate, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, camphoric acid and ammonium persulfate.
The product 5 and the oxidant in the step (6) are preferably calculated according to the molar ratio of 1: 1-20.
The reaction described in step (6) is preferably: reacting at room temperature for 24-48 h; more preferably 20-35 ℃ for 24-48 h.
An organic soluble high-conductivity multi-arm thiophene polymer is prepared by the preparation method.
The organic soluble high-conductivity multi-arm thiophene polymer is applied to the field of high-molecular conductive materials.
Compared with the prior art, the invention has the following advantages and effects:
(1) according to the invention, the multi-arm thiophene polymer is constructed, so that the thiophene polymer is soluble in an organic solution and keeps higher conductivity. In the invention, the annular silsesquioxane is used as a pivot, and a plurality of polythiophene chain segments extend out. The multi-arm structure breaks the local order of the molecules while increasing the length of the chain segment, so that the aggregation state of the molecules is changed, the order and the crystallinity of the molecules are reduced, the solubility in an organic solvent is realized, and the high conductivity is kept.
(2) The polymer designed by the invention has unique structure and mild reaction conditions. By controlling the type and dosage of the oxidant, the obtained polymer chain (in organic solutions such as dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), Tetrahydrofuran (THF), Trichloromethane (TCM), Dichloromethane (DCM) and the like has excellent solubility and higher conductivity.
(3) The invention constructs a multi-arm thiophene polymer by using tetravinyl silsesquioxane as a reaction core, and realizes organic solubility and high conductivity. In the invention, four vinyl annular silsesquioxane is used as a reaction core, four conductive polythiophene long chains are grown to construct a multi-arm thiophene polymer with a special space structure, the four polymer chains in a solvent are spread and separated to the greatest extent in different directions by taking the annular silsesquioxane as a center, and the four polymer chains are increased to a certain extentThe conjugated length of the chain segment simultaneously destroys the regularity of the molecule, reduces the local crystallization degree of the molecule and increases the dissolving capacity in organic solvents (excellent solubility and stability in organic solutions such as N, N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), Tetrahydrofuran (THF), Trichloromethane (TCM), Dichloromethane (DCM) and the like). Through the spatial inter-chain synergistic effect, the energy gap of low molecular orbit is effectively reduced, the intramolecular electron transmission and the intermolecular electron step are facilitated, the material has excellent conductivity, and when a PET film is used as a substrate wire rod for blade coating, the transmittance is kept at 80%, and the conductivity can reach 1.5 multiplied by 10-2S/cm. When glass is used as a substrate for spraying, the highest conductivity can reach 1.26S/cm.
Drawings
FIG. 1 is a graph showing the results of the dissolution of the organic soluble highly conductive multi-arm thiophene polymer obtained in example 1 in different organic solvents.
FIG. 2 is a graph showing the results of the conductivity of the organic soluble highly conductive multi-arm thiophene polymer obtained in example 1 in different organic solvents; wherein, the drawing a is a drawing of a bar coating result with a PET film as a substrate; and b is a graph of the spraying result using glass as a substrate.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
A preparation method of an organic soluble high-conductivity multi-arm thiophene polymer comprises the following steps:
(1) dissolving 0.1mol of vinyltriethoxysilane in 60mL of a mixed solution of dichloromethane and isopropanol (the volume ratio of the dichloromethane to the isopropanol is 1:1) to obtain a mixed solution 1; dissolving 0.1mol of potassium methoxide in 180mL of mixed solution of dichloromethane and isopropanol (the volume ratio of the dichloromethane to the isopropanol is 1:1) to obtain mixed solution 2; placing the mixed solution 2 in a 500mL round-bottom flask, adding 2g of water, magnetically stirring, slowly adding the mixed solution 1 into the mixed solution 2 through a constant-pressure funnel (the dropping speed is 3-5 drops per second), and reacting for 24 hours to obtain a product 1;
(2) adding 10mL of concentrated hydrochloric acid (36%) into the product 1 to adjust the pH value to 3-5, continuing to magnetically stir in a nitrogen environment, and reacting at room temperature for 24 hours to obtain a product 2;
(3) filtering the product 2, adding a saturated sodium bicarbonate solution into the filtrate, adjusting the pH to be neutral, adding excessive anhydrous magnesium sulfate, and drying to remove water; filtering to obtain filtrate, rotary evaporating at 60 deg.C, and vacuum drying at 60 deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) respectively taking 2mmol (0.57g) of product 3, 1.28mmol (0.212g) of palladium-carbon, 3mmol (0.6g) of N, N-dicyclohexylmethylamine and 8mmol (2.6g) of 3-bromothiophene, adding into 60mL of N, N-dimethylformamide, and reacting at 100 ℃ for 48 hours under the argon atmosphere to obtain a product 4;
(5) filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5g), stirring at room temperature for 12h, filtering to obtain filtrate, removing the solvent, and drying to obtain a product 5; the reaction route is as follows:
(6) and adding 1mmol of product 5 into 10mL of cyclohexane to obtain a mixed solution 1, adding 12mmol of 3, 4-ethylenedioxythiophene and 12mol of ferric p-toluenesulfonate into 10mL of acetonitrile to obtain a mixed solution 2, putting the mixed solution 2 into a beaker, slowly adding the mixed solution 2 into the beaker filled with the mixed solution 1 along the cup wall, and reacting at room temperature for 24-48 h to obtain the organic soluble high-conductivity multi-arm thiophene polymer. The reaction route is as follows:
example 2
(1) 0.1mol of vinyl triethoxysilane is dissolved in 60mL of mixed solution of dichloromethane and isopropanol (the volume ratio of dichloromethane to isopropanol is 1:1) to obtain mixed solution 1, and 0.1mol of potassium methoxide is dissolved in 180mL of mixed solution of dichloromethane and isopropanol (the volume ratio of dichloromethane to isopropanol is 1:1) to obtain mixed solution 2; placing the mixed solution 2 in a 500mL round-bottom flask, adding 2g of water, magnetically stirring, slowly adding the mixed solution 1 into the mixed solution 2 through a constant-pressure funnel (the dropping speed is 3-5 drops per second), and reacting for 24 hours to obtain a product 1;
(2) adding 10mL of concentrated hydrochloric acid (36%) into the product 1 to adjust the pH value to 3-5, continuing to magnetically stir in a nitrogen environment, and reacting at room temperature for 24 hours to obtain a product 2;
(3) filtering the product 2, adding a saturated sodium bicarbonate solution into the filtrate, adjusting the pH to be neutral, adding excessive anhydrous magnesium sulfate, and drying to remove water; filtering to obtain filtrate, rotary evaporating at 60 deg.C, and vacuum drying at 60 deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) respectively taking 2mmol (0.57g) of product 3, 1.28mmol (0.212g) of palladium-carbon, 3mmol (0.6g) of N, N-dicyclohexylmethylamine and 8mmol (2.6g) of 2-bromothiophene, adding into 60mL of N, N-dimethylformamide, and reacting at 100 ℃ for 48 hours under the argon atmosphere to obtain a product 4;
(5) filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5g), stirring at room temperature for 12h, filtering to obtain filtrate, removing the solvent, and drying to obtain a product 5; the reaction route is as follows:
(6) adding 10mL of cyclohexane into 1mmol of product 5 to obtain a mixed solution 1; adding 12mmol of 3, 4-ethylenedioxythiophene and 12mol of ferric p-toluenesulfonate into 10mL of acetonitrile to obtain a mixed solution 2, putting the mixed solution 2 into a beaker, slowly adding the mixed solution 2 into the beaker filled with the mixed solution 1 along the wall of the beaker, and reacting at room temperature for 24-48 h to obtain the organic soluble high-conductivity multi-arm thiophene polymer. The reaction route is as follows:
comparative example 1
A preparation method of an organic soluble high-conductivity multi-arm thiophene polymer comprises the following steps:
(1) dissolving 0.1mol of vinyl triethoxysilane in 60mL of a mixed solution of dichloromethane and isopropanol (the volume ratio of dichloromethane to isopropanol is 1:1) to obtain a mixed solution 1, dissolving 0.1mol of potassium methoxide in 180mL of a mixed solution of dichloromethane and isopropanol (the volume ratio of dichloromethane to isopropanol is 1:1) to obtain a mixed solution 2, placing the mixed solution 2 in a 500mL round-bottom flask, adding 2g of water, magnetically stirring, slowly adding the mixed solution 1 into the mixed solution 2 through a constant-pressure funnel (the dropping speed is 3-5 drops per second), and reacting for 24 hours to obtain a product 1;
(2) adding 10mL of concentrated hydrochloric acid (36%) into the product 1 to adjust the pH value to 3-5, continuing to magnetically stir in a nitrogen environment, and reacting at room temperature for 24 hours to obtain a product 2;
(3) filtering the product 2, adding a saturated sodium bicarbonate solution into the filtrate, adjusting the pH to be neutral, adding excessive anhydrous magnesium sulfate, and drying to remove water; filtering to obtain filtrate, rotary evaporating at 60 deg.C, and vacuum drying at 60 deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) respectively taking 2mmol (0.57g) of product 3, 1.28mmol (0.212g) of palladium-carbon, 3mmol (0.6g) of N, N dicyclohexylmethylamine and 8mmol (2.6g) of 3-bromothiophene, adding into 60mL of N, N-dimethylformamide, and reacting at 100 ℃ for 48 hours under the argon atmosphere to obtain a product 4;
(5) filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5g), stirring at room temperature for 12h, filtering to obtain filtrate, removing the solvent, and drying to obtain a product 5;
(6) adding 1mmol of product 5, 12mmol of 3, 4-ethylenedioxythiophene and 12mol of ferric p-toluenesulfonate into 10mL of acetonitrile at room temperature, and magnetically stirring for 48h to obtain the organic soluble high-conductivity multi-arm thiophene polymer.
Comparative example 2
A preparation method of an organic soluble high-conductivity multi-arm thiophene polymer comprises the following steps:
(1) dissolving 0.1mol of vinyl triethoxysilane in 60mL of mixed solution of dichloromethane and isopropanol (the volume ratio of the dichloromethane to the isopropanol is 1:1) to obtain mixed solution 1; dissolving 0.1mol of potassium methoxide in 180mL of mixed solution of dichloromethane and isopropanol (the volume ratio of the dichloromethane to the isopropanol is 1:1) to obtain mixed solution 2; placing the mixed solution 2 in a 500mL round-bottom flask, adding 2g of water, magnetically stirring, slowly adding the mixed solution 1 into the mixed solution 2 through a constant-pressure funnel (the dropping speed is 3-5 drops per second), and reacting for 24 hours to obtain a product 1;
(2) adding 10mL of hydrochloric acid (concentrated) into the product 1 to adjust the pH value to 3-5, continuing to magnetically stir in a nitrogen environment, and reacting at room temperature for 24 hours to obtain a product 2;
(3) filtering the product 2, adding a saturated sodium bicarbonate solution into the filtrate, adjusting the pH to be neutral, adding excessive anhydrous magnesium sulfate, and drying to remove water; filtering to obtain filtrate, rotary evaporating at 60 deg.C, and vacuum drying at 60 deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) respectively taking 2mmol (0.57g) of product 3, 1.28mmol (0.212g) of palladium-carbon, 3mmol (0.6g) of N, N-dicyclohexylmethylamine and 8mmol (2.6g) of 2-bromothiophene, adding into 60mL of N, N-dimethylformamide, and reacting at 100 ℃ for 48 hours under the argon atmosphere to obtain a product 4;
(5) filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5g), stirring at room temperature for 12h, filtering to obtain filtrate, removing the solvent, and drying to obtain a product 5;
(6) adding 1mmol of product 5, 12mmol of 3, 4-ethylenedioxythiophene and 12mol of ferric p-toluenesulfonate into 10mL of acetonitrile at room temperature, and magnetically stirring for 48 hours to obtain the organic soluble high-conductivity multi-arm thiophene polymer.
Performance testing
(1) And (3) testing the dissolution property:
the organic-soluble high-conductivity multi-arm thiophene polymer prepared in example 1 was placed in N-methyl-pyrrolidone (NMP), N-Dimethylformamide (DMF), chloroform (TCM), Dichloromethane (DCM), and Tetrahydrofuran (THF), and the dissolution of the organic-soluble high-conductivity multi-arm thiophene polymer in the above solvents was observed;
division criteria for solubility:
well: the mass concentration is not less than 20 mg/mL; preferably: 20mg/mL > mass concentration ≧ 10 mg/mL; in general: the mass concentration of 10mg/mL is not less than 5 mg/mL; difference: 5mg/mL > mass concentration.
Division criteria for stability:
the following steps are good: the solution with the mass concentration of ≧ 20mg/mL is kept still for more than 60 days without visible precipitation and suspended matters;
preferably: the standing time of the solution with the mass concentration of 20mg/mL being not less than 10mg/mL is more than 30 days but not more than 60 days, and no visible precipitation and suspended matters are generated;
in general: the solution with the mass concentration of 10mg/mL being not less than 5mg/mL is kept still for more than 15 days but not more than 30 days, and no visible precipitation and suspended matters are generated;
difference: the 5mg/mL > mass concentration solution was allowed to stand for more than 1 day but not more than 15 days without visible precipitation and generation of suspended matter.
The results are shown in Table 1 and FIGS. 1-2:
table 1:
| solvent(s) | Colour(s) | Solubility in water | Stability of |
| N-methyl-pyrrolidone (NMP) | Reddish brown color | Good taste | Good taste |
| N, N-dimethylformamide(DMF) | Brown yellow | Good taste | Good taste |
| Trichloromethane (TCM) | Yellow green | Good taste | Good taste |
| Dichloromethane (DCM) | Yellow green | In general terms | In general |
| Tetrahydrofuran (THF) | Yellow colour | In general | In general |
As can be seen from table 1, the organic soluble highly conductive multi-arm thiophene polymer prepared by the method described in the present application has excellent solubility and stability in organic solvents of N, N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), Tetrahydrofuran (THF), Trichloromethane (TCM), and Dichloromethane (DCM).
(2) And (3) testing the conductivity:
and (3) conductivity measurement: a four-probe method;
and (3) transmittance measurement: ultraviolet-visible spectrophotometry;
the results are shown in FIG. 2, and it was found that: as shown in FIG. 2a, when the PET film is used as a base wire rod for knife coating, the conductivity can reach 1.5 x 10 when the transmittance is kept 80 percent-2S/cm. When the glass is used as a substrate for spraying, the highest conductivity can reach 1.26S/cm (as shown in figure 2 b).
The organic soluble highly conductive multi-arm thiophene polymers prepared in examples 1-2 and comparative examples 1-2 were subjected to conductivity tests in the above-described manner, respectively, and the results were as follows:
TABLE 2
| Sample (I) | Conductivity (transmittance at 80%) | Spraying of paint |
| Example 1 | 1.5×10-2S/cm | 1.26S/cm |
| Example 2 | 8.2×10-3S/cm | 0.97S/cm |
| Comparative example 1 | 1.4×10-2S/cm | 1.22S/cm |
| Comparative example 2 | 8.3×10-3S/cm | 0.95S/cm |
As can be seen from table 2, the conductivity properties of the two multi-arm structures 1 are close, and the conductivity increases with decreasing transmittance.
The yields of the organic soluble highly conductive multi-arm thiophene polymers obtained in examples 1-2 and comparative examples 1-2 are shown in table 3:
TABLE 3
| Sample (I) | Yield (step 6 yield only) |
| Example 1 | 81％ |
| Comparative example 1 | 68％ |
| Example 2 | 79％ |
| Comparative example 2 | 68％ |
As can be seen from Table 3, the examples have a greater improvement in productivity than the comparative example, step (6), in which interfacial polymerization was used.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an organic soluble high-conductivity multi-arm thiophene polymer is characterized by comprising the following steps:
(1) dissolving vinyl triethoxysilane in a mixed solution of dichloromethane and isopropanol to obtain a mixed solution 1; dissolving potassium alcoholate in a mixed solution of dichloromethane and isopropanol to obtain a mixed solution 2; adding water into the mixed solution 2, stirring, slowly adding the mixed solution 1 into the water to obtain a mixed solution 2, magnetically stirring, and reacting to obtain a product 1;
(2) adding protonic acid into the product 1, adjusting the pH value to acidity, and continuing to magnetically stir in a nitrogen environment for reaction to obtain a product 2;
(3) filtering the product 2, adding a saturated sodium bicarbonate solution into the filtrate of the product 2 to adjust the pH value to be neutral, and adding an excessive drying agent to remove water; filtering to obtain filtrate, performing rotary evaporation, and performing vacuum drying to obtain a product 3;
(4) respectively taking the product 3, a palladium catalyst,AlkaliAdding bromothiophene and bromothiophene into N, N-dimethylformamide, and reacting under the atmosphere of argon to obtain a product 4;
(5) filtering the product 4, taking the filtrate of the product 4, adding N-acetyl-L-cysteine, stirring, filtering to obtain the filtrate, removing the solvent, and drying to obtain a product 5;
(6) adding cyclohexane into the product 5 to obtain a mixed solution 1; adding a thiophene derivative and an oxidant into acetonitrile to obtain a mixed solution 2; and slowly adding the mixed solution 2 into the mixed solution 1, and reacting to obtain the organic soluble high-conductivity multi-arm thiophene polymer.
2. The method according to claim 1, wherein the potassium alkoxide in the step (1) includes at least one of potassium tert-butoxide and potassium methoxide;
in the mixed solution of dichloromethane and isopropanol in the step (1), the dichloromethane and the isopropanol are calculated according to the volume ratio of 1: 1;
calculating the vinyl triethoxysilane and potassium alcoholate in the step (1) according to the molar ratio of 1: 1;
the ratio of the water to the mixed solution 2 in the step (1) is calculated according to the mass-to-volume ratio of 2: 180.
3. The production method according to claim 1,
the protonic acid in the step (2) is hydrochloric acid;
the acidity in the step (2) is pH 3-5;
the reaction time in the step (2) is 24-48 h at room temperature.
4. The production method according to claim 1,
the drying agent in the step (3) is anhydrous magnesium sulfate;
the temperature of the rotary evaporation in the step (3) is 50-70 ℃;
and (4) drying in vacuum in the step (3) at the temperature of 50-70 ℃ for 12-48 h.
5. The method according to claim 1,
calculating the product 3, the palladium catalyst, the alkali and the bromothiophene in the step (4) according to the mol ratio of 2:1.28:3: 8;
the palladium catalyst in the step (4) is palladium carbon;
the base in the step (4) is preferably N, N dicyclohexylmethylamine;
the bromothiophene in the step (4) is at least one of 2-bromothiophene and 3-bromothiophene.
6. The production method according to claim 1,
the mass g/volume/mL ratio of the N-acetyl-L-cysteine to the filtrate of the product 4 in the step (5) is preferably 0.05-0.1: 1;
and (5) stirring at room temperature for 12-24 hours.
7. The production method according to claim 1,
the ratio of the product 5 to the cyclohexane in the step (6) by mol mmol to the volume mL is calculated to be 0.05-0.2: 1;
calculating the cyclohexane and the acetonitrile in the step (6) according to the volume ratio of 1: 1;
the thiophene derivative in the step (6) includes but is not limited to at least one of thiophene, 3, 4-ethylenedioxythiophene and 3, 4-propylenedioxythiophene;
and (4) calculating the product 5 and the thiophene derivative in the step (6) according to the molar ratio of 1: 8-20.
8. The production method according to claim 1,
the oxidant in the step (6) includes but is not limited to at least one of ferric trichloride, ferric dodecyl benzene sulfonate, ferric p-toluene sulfonate, dodecylbenzene sulfonic acid, p-toluene sulfonic acid, camphoric acid and ammonium persulfate;
calculating the product 5 and the oxidant in the step (6) according to the molar ratio of 1: 1-20;
the reaction in the step (6) is as follows: reacting at room temperature for 24-48 h.
9. An organic soluble high-conductivity multi-arm thiophene polymer, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The use of the organic soluble highly conductive multi-arm thiophene polymer of claim 9 in the field of high molecular conductive materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011552215.6A CN114672001B (en) | 2020-12-24 | 2020-12-24 | Organic soluble high-conductivity multi-arm thiophene polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011552215.6A CN114672001B (en) | 2020-12-24 | 2020-12-24 | Organic soluble high-conductivity multi-arm thiophene polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114672001A true CN114672001A (en) | 2022-06-28 |
| CN114672001B CN114672001B (en) | 2024-01-09 |
Family
ID=82070535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011552215.6A Active CN114672001B (en) | 2020-12-24 | 2020-12-24 | Organic soluble high-conductivity multi-arm thiophene polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672001B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517958B1 (en) * | 2000-07-14 | 2003-02-11 | Canon Kabushiki Kaisha | Organic-inorganic hybrid light emitting devices (HLED) |
| KR20090060110A (en) * | 2007-12-06 | 2009-06-11 | 광 석 서 | Organic solvent dispersible thiophene conductive polymer complex and conductive polymer dispersion |
| CN111232957A (en) * | 2020-01-15 | 2020-06-05 | 广东省石油与精细化工研究院 | Carbon material dispersant, and preparation method and application thereof |
-
2020
- 2020-12-24 CN CN202011552215.6A patent/CN114672001B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517958B1 (en) * | 2000-07-14 | 2003-02-11 | Canon Kabushiki Kaisha | Organic-inorganic hybrid light emitting devices (HLED) |
| KR20090060110A (en) * | 2007-12-06 | 2009-06-11 | 광 석 서 | Organic solvent dispersible thiophene conductive polymer complex and conductive polymer dispersion |
| CN111232957A (en) * | 2020-01-15 | 2020-06-05 | 广东省石油与精细化工研究院 | Carbon material dispersant, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| KUEI-BAI CHEN等: "Synthesis and Opto-electrical Properties of Stellar Polyfluorene Derivatives Containing Polyhedral Oligomeric Silsesquioxanes as the Center Core", 《JORNAL OF POLYMER RESEARCH》, vol. 13, no. 3, pages 237 - 245, XP019251114, DOI: 10.1007/s10965-005-9031-9 * |
| S.A.PONOMARENKO等: "Bithiophenesilane-Based Dendronized Polymers:Facile Synthesis and Properties of Novel Highly Branched Organosilicon Macromolecular Structures", 《MACROMOLECULES》, vol. 45, no. 4, pages 2014 - 2024 * |
| 胡小勇等: "可溶性笼形倍半硅氧烷共轭聚合物作为一种高效的单壁碳纳米管分散剂", 《广东化工》, vol. 2, no. 2, pages 1 - 3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114672001B (en) | 2024-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1605007B1 (en) | Processes to prepare oligomeric thiophene compounds | |
| WO2011075644A2 (en) | Copolymers of 3,4-dialkoxythiophenes and methods for making and devices | |
| EP2927258A1 (en) | Benzodithiophene based copolymer containing thieno [3,4-b]thiophene units and preparing method and applications thereof | |
| KR20170109622A (en) | Related Design Strategies to Increase Molecular Weight of DPPs and Semi-Conjugated Copolymers Having Fused Thiophenes Having Branched Alkyl-Chains and / or Branched Alkyl-Chains | |
| EP2927259B1 (en) | Benzodithiophene based copolymer containing thiophene pyrroledione units and preparing method and applications thereof | |
| US9328203B2 (en) | Benzodithiophene based copolymer containing pyridino [2,1,3] thiadiazole units and preparing method and applications thereof | |
| CN107189083B (en) | Conductive polymer PEDOT organic dispersion system and preparation method thereof | |
| CN114672001B (en) | Organic soluble high-conductivity multi-arm thiophene polymer and preparation method and application thereof | |
| US5908583A (en) | Semiconductor polymer | |
| EP2412770A1 (en) | Electroconductive coating composition and process for production of electroconductive coating film | |
| CN110872376B (en) | Cyclized indigo receptor and polymer as well as preparation method and application thereof | |
| CN108516978B (en) | Asymmetric porphyrin organic micromolecule cathode interface material and preparation method and application thereof | |
| CN107840944B (en) | Random copolymer with difluoro benzothiadiazole and bitetrathiophene as main chains and preparation method and application thereof | |
| CN113861389B (en) | Polymer semiconductors containing quinone-donor-acceptor units, their preparation and use | |
| CN110283098B (en) | Star-shaped aromatized inorganic acid radical semiconductor material and preparation and application thereof | |
| CN110498793B (en) | Small-molecule photovoltaic bulk phase material based on rhodanine and application thereof | |
| US9328194B2 (en) | Benzodithiophene based copolymer containing isoindoline-1,3-diketone units and preparing method and applications thereof | |
| CN114672000B (en) | Linear high-conductivity organic soluble thiophene polymer and preparation method and application thereof | |
| JPH02218716A (en) | Organic semiconductor and production thereof | |
| Jiang et al. | Ethynylene‐Linked Oligomers Based on Benzodithiophene: Synthesis and Photoelectric Properties | |
| WO2020046669A1 (en) | Semiconducting co-polymers of methylenedihydropyrazines with fused thiophenes | |
| CN114634791B (en) | Poly-o-epoxy-N-methylaniline conductive adhesive resin, preparation method thereof, conductive organic thermosetting material and application | |
| CN112574645B (en) | Modified polyaniline anticorrosive paint and preparation method thereof | |
| CN109912783B (en) | Polymer electron acceptor material, preparation method thereof and application thereof in polymer solar cell | |
| CN113817141A (en) | Copolymer of EDOT and (hetero) arene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |