CN114672001B - 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
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- CN114672001B CN114672001B CN202011552215.6A CN202011552215A CN114672001B CN 114672001 B CN114672001 B CN 114672001B CN 202011552215 A CN202011552215 A CN 202011552215A CN 114672001 B CN114672001 B CN 114672001B
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- 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 48
- 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 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 75
- 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 238000003756 stirring 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
- 238000000034 method Methods 0.000 claims description 13
- 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 10
- 238000001035 drying Methods 0.000 claims description 10
- 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 8
- 238000010025 steaming 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
- 239000012300 argon atmosphere Substances 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
- -1 potassium alkoxide Chemical class 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
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 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
- 239000004020 conductor Substances 0.000 claims description 4
- 239000002274 desiccant Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 3
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- 230000002378 acidificating effect Effects 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
- 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
- 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 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 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 15
- 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
- 239000000203 mixture 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
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 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 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 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 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000012360 testing method Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001276 controlling effect 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
- 230000000694 effects Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- 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
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
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- C08G2261/50—Physical properties
- C08G2261/59—Stability
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- 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
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The invention discloses an organic soluble high-conductivity multi-arm thiophene polymer and a preparation method and application thereof, belonging 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 types and dosage of the oxidizing agent, the obtained polymer chain has excellent solubility in organic solutions such as dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), tetrahydrofuran (THF), trichloromethane (TCM), dichloromethane (DCM) and the like, and has higher conductive performance.
Description
Technical Field
The invention belongs to the technical field of preparation of thiophene conductive high-molecular polymers and novel high-molecular functional materials, and particularly relates to an organic soluble high-conductivity multi-arm thiophene polymer, and a preparation method and application thereof.
Background
In recent years, the polymer has been receiving attention, and has properties of high molecular materials such as foldability, high flexibility, high elasticity and high plasticity, and at the same time, has a high conjugated structure, so that electrons can be transmitted in molecules and between molecules, thereby having the property of a conductor. At present, common organic polymer materials include polyaniline, polyacetylene, polypyrrole, polythiophene and the like. The polythiophene has the advantages of high conductivity, easy oxidation synthesis and stable chemical property, and becomes the polymer conductive material with the most research and application at present. The material is widely applied to various fields such as organic solar batteries, antistatic coatings, super capacitors, flexible display screens, intelligent windows, field emission transistors and the like, has huge development space, and is a star material which is widely focused in the scientific and technological industry in recent years.
However, the high conjugated structure increases the rigidity of the molecular chain, and the refractory and indissolvable property is unfavorable for processing, so that the application of the polymer in various scenes is limited. Most of the current market application is aqueous dispersion of polythiophene, and the existence of water in electronic devices can corrode the components, so that the service life of the components is shortened, and great potential safety hazards are brought to the operation of the components. Therefore, an organic dispersible thiophene polymer becomes a hot content for research and development in recent years, and has wide application development potential.
At present, in order to realize the dispersion of thiophene polymers in an organic system, a side chain engineering is mostly adopted to introduce soluble alkyl groups or alkoxy groups and the like on thiophene rings or epoxy rings, and the defects of complex preparation process, strict reaction condition requirements, low conductivity, low solubility and the like exist, so that a certain gap exists for large-scale application of the thiophene polymers.
Disclosure of Invention
The invention aims at providing a preparation method of an organic soluble high-conductivity multi-arm thiophene polymer aiming at the defects of insoluble and refractory thiophene polymer, complex preparation process, harsh reaction conditions and the like.
Another object of the present invention is to provide an organic soluble high conductivity multi-arm thiophene polymer prepared by the above preparation method. The thiophene polymer prepared by the invention has higher solubility in organic solution, good stability and higher conductivity.
It is a further object of the present invention to provide the use of the above-described organic soluble highly conductive multi-arm thiophene polymers.
The aim of the invention is achieved by the following technical scheme:
a preparation method of an organic soluble high-conductivity multi-arm thiophene polymer comprises the following steps:
(1) Dissolving vinyltriethoxysilane in a mixed solution of dichloromethane and isopropanol to obtain a mixed solution 1; dissolving potassium alkoxide 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 mixed solution 2 after adding water, magnetically stirring, and reacting to obtain a product 1;
(2) Adding protonic acid into the product 1, adjusting the pH to be acidic, and continuing magnetic stirring in a nitrogen environment to react to obtain a product 2;
(3) Filtering the product 2, adding saturated sodium bicarbonate solution into the filtrate of the product 2 to adjust the pH to be neutral, and adding excessive drying agent to remove water; filtering to obtain filtrate, rotary steaming, and vacuum drying to obtain product 3 (tetravinyl silsesquioxane);
(4) Respectively taking a product 3, a palladium catalyst, alkali and bromothiophene, adding the product into N, N-dimethylformamide, and reacting the mixture under the argon atmosphere to obtain a product 4 (tetrathiophene-vinyl silsesquioxane);
(5) Filtering the product 4, taking filtrate of the product 4, adding N-acetyl-L-cysteine, stirring, filtering to obtain filtrate, removing 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; 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 in step (1) preferably includes at least one of potassium t-butoxide and potassium methoxide.
In the mixed solution of dichloromethane and isopropanol in the step (1), the dichloromethane and the isopropanol are preferably calculated according to 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 mixed solution 2 in step (1) is preferably calculated as a mass (g) to volume (mL) ratio of 2:180.
The reaction time in the step (1) is preferably 12 to 48 hours; more preferably 24 to 48 hours.
The protonic acid in step (2) is preferably hydrochloric acid; more preferably concentrated hydrochloric acid having a concentration of 36%.
The acidity in the step (2) means that the pH is 3 to 5.
The reaction time in the step (2) is preferably 24-48 hours at room temperature; more preferably at 25 to 35 ℃ for 24 to 48 hours.
The drying agent in the step (3) is preferably anhydrous magnesium sulfate.
The temperature of the rotary evaporation 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 hours; more preferably 60℃for 24 hours.
The product 3, palladium catalyst, base and bromothiophene described in step (4) are preferably calculated in a molar ratio of 2:1.28:3:8.
The palladium catalyst 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 to 48 hours.
The filtrate of N-acetyl-L-cysteine and product 4 described in step (5) is preferably calculated as a mass (g) to volume (mL) ratio of 0.05 to 0.1:1.
The stirring in the step (5) is preferably stirring at room temperature for 12-24 hours; more preferably, the stirring is carried out at 25 to 35℃for 12 to 24 hours.
The product 5 and cyclohexane described in step (6) are preferably calculated as a molar (mmol) to volume (mL) ratio of 0.05 to 0.2:1.
The cyclohexane and acetonitrile in step (6) are preferably calculated in a 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 molar ratio of the product 5 to the thiophene derivative in the step (6) is preferably 1:8-20.
The oxidizing agent described in step (6) preferably includes, but is not limited to, at least one of ferric trichloride, ferric dodecylbenzenesulfonate, ferric p-toluenesulfonate, dodecylbenzenesulfonate, p-toluenesulfonate, camphoric acid, and ammonium persulfate.
The product 5 and the oxidant in step (6) are preferably calculated according to a molar ratio of 1:1-20.
The reaction described in step (6) is preferably: reacting for 24-48 h at room temperature; more preferably at 20 to 35 ℃ for 24 to 48 hours.
The organic soluble high-conductivity multi-arm thiophene polymer is prepared by the preparation method.
The application of the organic soluble high-conductivity multi-arm thiophene polymer in 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, by constructing the multi-arm thiophene polymer, the thiophene polymer is soluble in an organic solution and simultaneously keeps higher conductivity. In the invention, annular silsesquioxane is taken as a hinge, and a plurality of polythiophene chain segments extend. The multi-arm structure breaks the local order of the molecules while increasing the chain segment length, so that the aggregation state of the molecules is changed, the order and crystallinity of the molecules are reduced, the solubility of the molecules in an organic solvent is realized, and meanwhile, the higher conductivity is maintained.
(2) The polymer designed by the invention has unique structure and mild reaction conditions. By controlling the types and dosage of the oxidizing agent, the obtained polymer chain has excellent solubility in organic solutions such as dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), tetrahydrofuran (THF), trichloromethane (TCM), dichloromethane (DCM) and the like, and has higher conductive performance.
(3) The invention constructs a multi-arm thiophene polymer by taking tetravinyl silsesquioxane as a reaction core, so that the organic solubility is realized and the high conductivity is maintained. In the invention, tetravinyl annular silsesquioxane is taken as a reaction core, four conductive polythiophene long chains are grown, a multi-arm thiophene polymer with a special space structure is constructed, four polymer chains are stretched to the greatest extent in different directions by taking annular silsesquioxane as a center in a solvent, the conjugation length of chain segments is increased to a certain extent, the regularity of molecules is destroyed, and the local crystallization process is reducedThe solubility is increased, and the solubility in an organic solvent is increased (the solubility and stability in an organic solution such as N, N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), tetrahydrofuran (THF), chloroform (TCM), and Dichloromethane (DCM) are excellent). The energy gap of a low molecular orbit is effectively reduced through the synergistic effect between chains in space, which is beneficial to the electronic transmission in molecules and the electronic step between molecules, so that the material has excellent conductivity, and the conductivity can reach 1.5 multiplied by 10 when the PET film is used as a substrate wire rod for knife coating and the transmittance is kept 80 percent -2 S/cm. The highest conductivity of the glass used as a substrate can reach 1.26S/cm when the glass is sprayed.
Drawings
FIG. 1 is a graph showing the results of dissolution of the organic soluble highly conductive multi-arm thiophene polymer obtained in example 1 in various organic solvents.
FIG. 2 is a graph showing the results of conducting properties of the organic soluble highly conductive multi-arm thiophene polymer obtained in example 1 in different organic solvents; wherein, figure a is a drawing of the result of the knife coating with PET film as the substrate wire rod; FIG. b is a graph showing the result of spraying glass as a substrate.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
A preparation method of an organic soluble high-conductivity multi-arm thiophene polymer comprises the following steps:
(1) 0.1mol of vinyltriethoxysilane 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; 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 into 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 (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, regulating the pH to 3-5, and 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 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, steaming at 60deg.C, and vacuum drying at 60deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) 2mmol (0.57 g) of the product 3, 1.28mmol (0.212 g) of palladium-carbon, 3mmol (0.6 g) of N, N-dicyclohexylmethylamine and 8mmol (2.6 g) of 3-bromothiophene are respectively taken and added into 60mL of N, N-dimethylformamide, and the mixture is reacted for 48 hours at 100 ℃ under the argon atmosphere to obtain a product 4;
(5) Filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5 g), stirring at room temperature for 12h, filtering the 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 10mL of acetonitrile into 12mmol of 3, 4-ethylenedioxythiophene and 12mol of iron p-toluenesulfonate to obtain a mixed solution 2, putting the mixed solution 2 into a beaker, slowly adding the mixed solution 2 into the beaker containing the mixed solution 1 along the wall of the beaker, and reacting for 24-48 hours at room temperature to obtain the organic soluble high-conductivity multi-arm thiophene polymer. The reaction route is as follows:
example 2
(1) 0.1mol of vinyltriethoxysilane is dissolved in 60mL of mixed solution of dichloromethane and isopropanol (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 (volume ratio of dichloromethane to isopropanol is 1:1) to obtain mixed solution 2; placing the mixed solution 2 into 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 (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, regulating the pH to 3-5, and 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 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, steaming at 60deg.C, and vacuum drying at 60deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) 2mmol (0.57 g) of the product 3, 1.28mmol (0.212 g) of palladium-carbon, 3mmol (0.6 g) of N, N-dicyclohexylmethylamine and 8mmol (2.6 g) of 2-bromothiophene are respectively taken and added into 60mL of N, N-dimethylformamide, and the mixture is reacted for 48 hours at 100 ℃ under the argon atmosphere to obtain a product 4;
(5) Filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5 g), stirring at room temperature for 12h, filtering the filtrate, removing the solvent, and drying to obtain a product 5; the reaction route is as follows:
(6) Taking 1mmol of the product 5, and adding 10mL of cyclohexane to obtain a mixed solution 1; and adding 10mL of acetonitrile into 12mmol of 3, 4-ethylenedioxythiophene and 12mol of ferric p-toluenesulfonate to obtain a mixed solution 2, putting the mixed solution 2 into a beaker, slowly adding the mixed solution 2 into the beaker containing the mixed solution 1 along the wall of the beaker, and reacting for 24-48 hours at room temperature 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) 0.1mol of vinyltriethoxysilane 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, 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, the mixed solution 2 is placed in a 500mL round bottom flask, 2g of water is added, magnetic stirring is carried out, the mixed solution 1 is slowly added into the mixed solution 2 through a constant pressure funnel (the dropping speed is 3-5 drops per second), and the reaction is carried out for 24 hours to obtain a product 1;
(2) Adding 10mL of concentrated hydrochloric acid (36%) into the product 1, regulating the pH to 3-5, and 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 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, steaming at 60deg.C, and vacuum drying at 60deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) 2mmol (0.57 g) of the product 3, 1.28mmol (0.212 g) of palladium-carbon, 3mmol (0.6 g) of N, N dicyclohexylmethylamine and 8mmol (2.6 g) of 3-bromothiophene are respectively taken and added into 60mL of N, N-dimethylformamide, and the mixture is reacted for 48 hours at 100 ℃ under the argon atmosphere to obtain a product 4;
(5) Filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5 g), stirring at room temperature for 12h, filtering the filtrate, removing the solvent, and drying to obtain a product 5;
(6) Taking 1mmol of product 5, 12mmol of 3, 4-ethylenedioxythiophene and 12mol of iron p-toluenesulfonate, adding 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) 0.1mol of vinyltriethoxysilane 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; 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 into 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 (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 to 3-5, and continuing to magnetically stir in a nitrogen environment to react for 24 hours at room temperature to obtain a product 2;
(3) Filtering the product 2, adding 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, steaming at 60deg.C, and vacuum drying at 60deg.C for 24 hr to obtain product 3 (tetravinyl silsesquioxane) with the following structural formula;
(4) 2mmol (0.57 g) of the product 3, 1.28mmol (0.212 g) of palladium-carbon, 3mmol (0.6 g) of N, N-dicyclohexylmethylamine and 8mmol (2.6 g) of 2-bromothiophene are respectively taken and added into 60mL of N, N-dimethylformamide, and the mixture is reacted for 48 hours at 100 ℃ under the argon atmosphere to obtain a product 4;
(5) Filtering the product 4, taking 50mL of filtrate, adding N-acetyl-L-cysteine (5 g), stirring at room temperature for 12h, filtering the filtrate, removing the solvent, and drying to obtain a product 5;
(6) Taking 1mmol of the product 5, 12mmol of 3, 4-ethylenedioxythiophene and 12mol of iron p-toluenesulfonate, adding 10mL of acetonitrile at room temperature, magnetically stirring for 48 hours, and obtaining the organic soluble high-conductivity multi-arm thiophene polymer.
Performance testing
(1) Dissolution performance test:
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), respectively, and the dissolution of the organic soluble high conductivity multi-arm thiophene polymer in the above solvents was observed;
solubility partitioning criteria:
and (3) good: the mass concentration is not less than 20mg/mL; the method is better: 20mg/mL > mass concentration ∈ is equal to or greater than 10mg/mL; generally: 10mg/mL > mass concentration ∈ is equal to or greater than 5mg/mL; the difference is: 5mg/mL > mass concentration.
Stability partitioning criteria:
and (3) good: the solution with the mass concentration of not less than 20mg/mL is kept stand for more than 60 days without generation of macroscopic precipitate and suspended matters;
the method is better: 20mg/mL > solution with mass concentration of not less than 10mg/mL is kept stand for more than 30 days but not more than 60 days without macroscopic precipitation and suspended matters;
generally: 10mg/mL > solution with mass concentration of not less than 5mg/mL is kept stand for more than 15 days but not more than 30 days without macroscopic precipitation and suspended matters;
the difference is: the solution at a concentration of 5mg/mL > mass was allowed to stand for more than 1 day but not more than 15 days without visible precipitation and suspended matter generation.
The results are shown in Table 1 and FIGS. 1-2:
table 1:
| solvent(s) | Color of | Solubility of | Stability of |
| N-methyl-pyrrolidone (NMP) | Reddish brown | Good (good) | Good (good) |
| N, N-Dimethylformamide (DMF) | Brown yellow | Good (good) | Good (good) |
| Chloroform (TCM) | Yellow green | Good (good) | Good (good) |
| Dichloromethane (DCM) | Yellow green | In general | In general |
| Tetrahydrofuran (THF) | Yellow colour | In general | In general |
As can be seen from table 1, the organic soluble high-conductivity multi-arm thiophene polymer prepared by the method has excellent solubility and stability in N, N-Dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), tetrahydrofuran (THF), trichloromethane (TCM) and Dichloromethane (DCM) organic solvents.
(2) Conducting performance test:
conductivity measurement: a four-probe method;
transmittance measurement: ultraviolet visible spectrophotometry;
the results are shown in fig. 2, and found: as shown in FIG. 2a, the conductivity of the PET film used as a substrate bar can reach 1.5X10 when the transmittance is kept at 80% during knife coating -2 S/cm. The highest electrical conductivity of the glass-based spray coating can reach 1.26S/cm (see FIG. 2 b).
The organic soluble highly conductive multi-arm thiophene polymers prepared in examples 1-2 and comparative examples 1-2 were respectively subjected to conductive property test in the above manner, and the results were as follows:
TABLE 2
| Sample of | Conductivity (transmittance when 80% is maintained) | Spraying |
| Example 1 | 1.5×10 -2 S/cm | 1.26S/cm |
| Example 2 | 8.2×10 -3 S/cm | 0.97S/cm |
| Comparative example 1 | 1.4×10 -2 S/cm | 1.22S/cm |
| Comparative example 2 | 8.3×10 -3 S/cm | 0.95S/cm |
As can be seen from table 2, the conductivity of the two multi-arm structures 1 is 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 Table 3
| Sample of | Yield (refer to 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 productivity of the examples was greatly improved compared with the comparative example in which the interfacial polymerization method was used in the step (6).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the organic soluble high-conductivity multi-arm thiophene polymer is characterized by comprising the following steps:
(1) Dissolving vinyltriethoxysilane in a mixed solution of dichloromethane and isopropanol to obtain a mixed solution 1; dissolving potassium alkoxide 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 the mixed solution 2, magnetically stirring, and reacting to obtain a product 1;
(2) Adding protonic acid into the product 1, adjusting the pH to be acidic, and continuing magnetic stirring in a nitrogen environment to react to obtain a product 2;
(3) Filtering the product 2, adding saturated sodium bicarbonate solution into the filtrate of the product 2 to adjust the pH to be neutral, and adding excessive drying agent to remove water; filtering to obtain filtrate, rotary steaming, and vacuum drying to obtain product 3;
(4) Respectively adding the product 3, a palladium catalyst, alkali and bromothiophene into N, N-dimethylformamide, and reacting under the argon atmosphere to obtain a product 4;
(5) Filtering the product 4, taking filtrate of the product 4, adding N-acetyl-L-cysteine, stirring, filtering to obtain filtrate, removing 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; 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 of claim 1, wherein the potassium alkoxide in step (1) comprises at least one of potassium t-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;
the mol ratio of the vinyl triethoxysilane to the potassium alkoxide in the step (1) is 1:1;
the ratio of water to the mixed solution 2 in the step (1) is calculated according to the mass g volume mL ratio of 2:180.
3. The method according to claim 1, wherein,
the protonic acid in the step (2) is hydrochloric acid;
the acidity in the step (2) means that the pH is 3-5;
the reaction time in the step (2) is 24-48 and h at room temperature.
4. The method according to claim 1, wherein,
the drying agent in the step (3) is anhydrous magnesium sulfate;
the temperature of the rotary steaming in the step (3) is 50-70 ℃;
the temperature of the vacuum drying in the step (3) is 50-70 ℃ and the time is 12-48 h.
5. The method according to claim 1, wherein,
the product 3, palladium catalyst, base and bromothiophene in the step (4) are calculated according to the mol ratio of 2:1.28:3:8;
the palladium catalyst in the step (4) is palladium carbon;
the alkali in the step (4) is N, N dicyclohexylmethylamine;
the bromothiophene in the step (4) is at least one of 2-bromothiophene and 3-bromothiophene.
6. The method according to claim 1, wherein,
the ratio of N-acetyl-L-cysteine to the filtrate of the product 4 in the step (5) is calculated according to the mass g volume mL ratio of 0.05-0.1:1;
the stirring in the step (5) is stirring at room temperature of 12-24 h.
7. The method according to claim 1, wherein,
calculating the ratio of the product 5 to cyclohexane in the step (6) according to the mol mmol to the volume mL of 0.05-0.2:1;
the cyclohexane and acetonitrile in the step (6) are calculated according to the volume ratio of 1:1;
the thiophene derivative in the step (6) comprises at least one of thiophene, 3, 4-ethylenedioxythiophene and 3, 4-propylenedioxythiophene;
the mol ratio of the product 5 to the thiophene derivative in the step (6) is 1:8-20.
8. The method according to claim 1, wherein,
the oxidant in the step (6) comprises at least one of ferric trichloride, ferric dodecylbenzene sulfonate, ferric paratoluenesulfonate, dodecylbenzene sulfonic acid, paratoluenesulfonic acid, camphoric acid and ammonium persulfate;
the mol ratio of the product 5 to the oxidant in the step (6) is 1:1-20;
the reaction in step (6) is: the reaction is carried out at room temperature for 24-48 and h.
9. An organic soluble high-conductivity multi-arm thiophene polymer, which is characterized by being prepared by the preparation method according to any one of claims 1-8.
10. Use of the organic soluble highly conductive multi-arm thiophene polymer according to claim 9 in the field of high molecular conductive materials.
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