CN111285842A - Trifluoromethyl thiophene ethylene thiophene donor, polymer and application thereof - Google Patents
Trifluoromethyl thiophene ethylene thiophene donor, polymer and application thereof Download PDFInfo
- Publication number
- CN111285842A CN111285842A CN202010098740.9A CN202010098740A CN111285842A CN 111285842 A CN111285842 A CN 111285842A CN 202010098740 A CN202010098740 A CN 202010098740A CN 111285842 A CN111285842 A CN 111285842A
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- Prior art keywords
- formula
- polymer
- thiophene
- trifluoromethyl
- tvt
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- -1 Trifluoromethyl thiophene ethylene thiophene Chemical compound 0.000 title claims abstract description 16
- 230000005669 field effect Effects 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 8
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 5
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- QCAJADRKKXQEGQ-UHFFFAOYSA-J oxolane;titanium(4+);tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].C1CCOC1 QCAJADRKKXQEGQ-UHFFFAOYSA-J 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- AQTSNKXEMWZOGA-UHFFFAOYSA-L (2-methanidylphenyl)-bis(2-methylphenyl)phosphane;palladium(2+);diacetate Chemical compound [Pd+2].[Pd+2].CC([O-])=O.CC([O-])=O.CC1=CC=CC=C1P(C=1C(=CC=CC=1)[CH2-])C1=CC=CC=C1C.CC1=CC=CC=C1P(C=1C(=CC=CC=1)[CH2-])C1=CC=CC=C1C AQTSNKXEMWZOGA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000012546 transfer Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JIOVMLYJNWPYPJ-UHFFFAOYSA-N C=C.S1C=CC=C1.S1C=CC=C1 Chemical compound C=C.S1C=CC=C1.S1C=CC=C1 JIOVMLYJNWPYPJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
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- 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
- C08G61/124—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 nitrogen atom in the ring
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- 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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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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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
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
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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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- C—CHEMISTRY; METALLURGY
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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
- C08G2261/3241—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 nitrogen atoms as the only heteroatom, e.g. carbazole
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Abstract
The invention discloses a trifluoromethyl thiophene ethylene thiophene donor, a polymer thereof and application thereof. The structural formula of the trifluoromethyl thiophene ethylene thiophene donor is shown as a formula II, and the structural formula of the polymer containing the trifluoromethyl thiophene ethylene thiophene donor is shown as a formula I. The invention provides a CF3The TVT polymer has lower FMO energy level, is beneficial to the injection and transmission of single electrons, and can be used for preparing a high-performance pure n-type field effect transistor device; with the present invention CF3The organic field effect transistor prepared by taking the TVT polymer as the semiconductor layer has higher mobility (mu) and on-off ratio (the electron mobility is up to 1.37 cm)2V‑1s‑1) In a single n-type OFETs has good application prospect.
Description
Technical Field
The invention relates to a trifluoromethyl thiophene ethylene thiophene donor, a polymer thereof and application thereof, belonging to the field of materials.
Background
Organic field-effect transistors (OFETs) are a class of Organic electronic devices. One of the cores is an organic semiconductor layer, which can be an organic small molecule material or an organic polymer material. Among them, organic polymer materials have received more and more attention due to their characteristics of low cost, large-area preparation, and preparation of fully flexible electronic devices, and have become a hot point of research. In recent years, Donor-Acceptor (Donor-Acceptor) type polymer semiconductor materials have become an effective means for synthesizing materials having high mobility. Organic semiconductor materials can be classified into p-type, n-type, and bipolar materials according to carrier transport characteristics, and carriers thereof are holes, electrons, holes, and electrons, respectively. Most of the current high-performance polymer organic semiconductor materials are p-type materials and bipolar materials, and the development of high-performance n-type materials is delayed.
Disclosure of Invention
The invention aims to provide a polymer of thiophene ethylene thiophene ((E) -1,2-di (thiophenyl-2-yl) ethane, TVT for short) donor with trifluoromethyl, which can be used for preparing an organic semiconductor layer in an organic field effect transistor.
The polymer provided by the invention has a lower Lowest Unoccupied Molecular Orbital (LUMO) energy level, is beneficial to the injection of electrons, and also has a very low Highest Occupied Molecular Orbital (HOMO) energy level, so that the transmission of holes is effectively prevented, and test results show that the polymer shows an excellent single n-type transmission characteristic. The trifluoromethyl TVT donor expands the variety of n-type materials and has good application prospect.
The invention provides, first, a compound of formula II, i.e., CF3TVT donor:
CF3the TVT donor can be prepared as follows:
a) taking ruthenium terpyridyl hexahydrate and cuprous acetate as catalysts, taking potassium carbonate as alkali, and reacting 2-formaldehyde thiophene-3-boric acid with iodotrifluoromethane in a DMF (N, N-dimethylformamide) solvent under the excitation of blue visible light to obtain 2-formaldehyde thiophene-3-trifluoromethyl shown in a formula II-a;
b) adding the 2-formaldehyde thiophene-3-trifluoromethyl shown in the formula II-a obtained in the step a) and zinc powder into a tetrahydrofuran solvent, and obtaining trifluoromethyl thiophene ethylene thiophene (namely CF) shown in the formula II under the catalysis of titanium tetrachloride or tetrahydrofuran titanium chloride3TVT)。
In the step a) of the method, the feeding molar ratio of the 2-formaldehyde thiophene-3-boric acid to the trifluoroiodomethane is 1: 2-10, specifically 1: 5; calculated by taking boric acid as one molar equivalent, the using amount of the alkali is 1-3 equivalents, the using amount of ruthenium terpyridyl hexahydrate is 0.01-0.1 equivalent, and the using amount of cuprous acetate is 0.05-0.5 equivalent; in the reaction step, the temperature is 60-80 ℃, the time is 12-24 hours, for example, the reaction is carried out for 12 hours at 60 ℃;
in the step b) of the method, the feeding molar ratio of the 2-formaldehyde thiophene-3-trifluoromethyl, the tetrahydrofuran titanium chloride and the zinc powder is 1: 2.5-5: 5-10; in the reaction step, the temperature is 70-100 ℃ and the time is 2-4 hours.
The invention provides a method for preparing a fluorine-containing polymer with CF3TVT-Donor CF3The structural formula of the TVT polymer is shown as the formula I:
in formula I, Acceptor represents an electron Acceptor group;
n represents a polymerization degree, is a natural number between 5 and 100, and specifically can be 10 to 40, more specifically 13 to 40, 13 to 20, or 18 to 40.
The structural formula of the electron acceptor group is shown as follows:
in the following formulas, the first and second groups,represents a substitution site, and R is a linear or branched alkyl group having 1 to 40 carbon atoms, preferably a linear or branched alkyl group having 16 to 37 or 24 carbon atoms.
The polymers provided by the present invention are preferably of the formula I-1 (IID-CF)3TVT) or formula I-2 (F-IID-CF)3TVT) polymer:
in the formula I-1, R is preferably a straight chain or branched chain alkyl of 1-40, preferably a straight chain or branched chain alkyl with 16-37 carbon atoms, and more preferably 4-decyl tetradecyl;
in the formula I-2, R is preferably a straight chain or branched alkyl group of 1-40, preferably a straight chain or branched alkyl group of 16-37 carbon atoms, and more preferably a 4-decyl tetradecyl group.
The invention also provides a preparation method of the polymer, which comprises the following steps:
carrying out polymerization reaction on the compound shown in the formula II and receptor monomers under the action of a catalyst and a ligand to obtain a polymer shown in the formula I;
the acceptor monomer is selected from any one of the following compounds:
in the above production method, the catalyst is at least one selected from the group consisting of Herrmann catalyst, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;
the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine and triphenylarsine.
In the preparation method, the molar ratio of the compound shown in the formula II, the receptor monomer, the catalyst and the ligand is 1: 1: 0.01-0.10: 0.04 to 0.80;
the temperature of the polymerization reaction is 90-140 ℃, and the time is 1 minute-24 hours.
The solvent for the polymerization reaction is at least one selected from the group consisting of toluene, chlorobenzene, and xylene.
The method may further comprise the following purification steps:
in the preparation method, after the polymerization reaction is finished, the obtained reaction system is cooled, then a mixed solvent of concentrated hydrochloric acid and methanol is added, the mixture is stirred for more than two hours at room temperature, then the mixture is filtered, the obtained precipitate is sequentially extracted by methanol, acetone, ethyl acetate and n-hexane by a Soxhlet extractor until the precipitate is colorless, micromolecules and a catalyst are removed, and the precipitate is extracted by trichloromethane to obtain the product; wherein, the volume ratio of the methanol to the hydrochloric acid can be specifically 20: 1, the concentration of hydrochloric acid may be 12M.
The polymer provided by the invention can be used for preparing an organic semiconductor layer in an organic field effect transistor, has higher mobility (mu) and on-off ratio, and has good application prospect in single n-type OFETs.
The invention has the following beneficial effects:
1. the polymerization method is C-H activated polymerization, the atom economy is high, and meanwhile, the device preparation process adopts non-chlorine solvents (toluene, xylene, tetralin and the like) for processing, so that the method has strong commercial application prospect;
2. the raw materials are commercial products, the synthetic route is simple, and compared with other synthetic methods, the synthetic route is green and efficient, and does not use and generate products polluting the environment. Meanwhile, the monomer and the polymer are new molecules, and can be popularized to the synthesis of polymers of various other receptors;
3、CF3the TVT polymer has lower FMO energy level, is favorable for single electron injection and transmission, and can be used for preparing high-performanceA pure n-type field effect transistor device of (1);
4. with the present invention CF3The organic field effect transistor prepared by taking the TVT polymer as the semiconductor layer has higher mobility (mu) and on-off ratio (the electron mobility is up to 1.37 cm)2V-1s-1) And has good application prospect in single n-type OFETs.
Drawings
FIG. 1 shows a polymer IID-CF3TVT (FIG. 1(a)) and F-IID-CF3UV-VIS absorption spectrum of TVT (FIG. 1 (b)).
FIG. 2 is a drawing of polymer IID-CF3TVT (FIG. 2(a)) and F-IID-CF3Cyclic voltammogram of TVT (fig. 2 (b)).
FIG. 3 is a CF of the present invention3The TVT polymer is a structural schematic diagram of an organic field effect transistor with a semiconductor layer.
FIG. 4 shows the polymer IID-CF according to the present invention3TVT (FIGS. 4(a) and 4(b)) and F-IID-CF3TVT (fig. 4(c) and 4(d)) is a graph of output characteristics and a graph of transfer characteristics of the polymer field effect transistor of the semiconductor layer.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 Compound (CF) of formula II3TVT) preparation
The synthetic route is as follows:
1) preparation of 2-Methylolthiophene-3-trifluoromethyl
In a glove box, 936 mg of 2-formaldehyde thiophene-3-boronic acid, 36.8 mg of cuprous acetate, 45 mg of ruthenium terpyridyl hexahydrate and 830 mg of potassium carbonate were added to a 100ml reaction tube. Then, an N, N-dimethylformamide solvent having 30 mmol of iodotrifluoromethane was added thereto. The reaction was carried out at 60 ℃ for 12 hours under the irradiation of a 30-watt blue LED lamp. Washing with water, extracting organic phase with ether, and separating by column chromatography to obtain the product. Pale yellow liquid (yield 36.8%).
In the reaction process, the molar ratio of the 2-formaldehyde thiophene-3-boric acid to the trifluoroiodomethane is 1: 5; calculated by taking boric acid as one molar equivalent, the dosage of the alkali is 1 equivalent, the dosage of the ruthenium terpyridyl hexahydrate is 0.01 equivalent, and the dosage of the cuprous acetate is 0.05 equivalent.
The structural characterization data is as follows:
1H NMR(400MHz,CDCl3)δppm 10.16(s,1H),7.78(d,J=4.0Hz,1H),7.38(d,J=8.0Hz,1H);13C NMR(100MHz,CDCl3)δppm 181.3(m),143.2(m),135.7(q,J=72 Hz),134.2,127.3(q,J=7.5Hz),121.7(q,J=541Hz);19F NMR(376MHz,CDCl3)δ ppm-54.9;HRMS(EI-TOF)m/z:[M+H]+Calculated for C6H3F3OS:179.9857;Found: 178.9854.
2) preparation of trifluoromethylthiopheneethylthiophene (i.e. CF of formula II)3TVT donor)
In a 100ml reaction flask, 1.66 g of tetrahydrofuran titanium chloride and 654 mg of activated zinc powder were added, and 10 ml of tetrahydrofuran solvent was further added, and heated under reflux at 70 ℃ for one hour. 360 mg of 2-formylthiophene-3-trifluoromethyl was dissolved in 2 ml of tetrahydrofuran, and the solution was added to the above reaction system while maintaining 70 degrees, followed by heating and refluxing for one hour. After the reaction is finished, cooling, pouring into silica gel, washing an organic phase by ethyl acetate, washing by water, extracting, and finally separating by column chromatography to obtain white solid CF3TVT (42.7% yield).
In the reaction process, the feeding molar ratio of the 2-formaldehyde thiophene-3-trifluoromethyl, the tetrahydrofuran titanium chloride and the zinc powder is 1: 2.5: 5.
the structural characterization data is as follows:
1H NMR(400MHz,CDCl3)δppm 7.35(s,2H),7.27(d,2H,J=3.6Hz),7.20(d,2H, J=3.6Hz);13C NMR(100MHz,CDCl3)δppm 142.2,128.5(q,J=67Hz),126.5,124.9, 122.5(q,J=540Hz),121.6;19F NMR(376MHz,CDCl3)δppm-56.3;HRMS(EI-TOF) m/z:[M+H]+Calculated for C12H6F6S2:327.9815;Found:327.9810.
example 2 Polymer IID-CF of formula I-13Preparation of TVT
Cyclized indigo-dibromo (as shown in formula III-1, R is 4-decyl tetradecyl) (110mg,0.1mmol), 3-trifluoromethyl-2 (2- (3-trifluoromethyl-2-thienylethylene) vinylthiophene) (32.8mg,0.1mmol), Herrmann's catalyst (2.4mg,0.002mmol), the ligand tri (o-tolyl) phosphine (1.4mg,0.004mmol), pivalic acid (10.2 mg,0.1mmol), cesium carbonate (98mg,0.3mmol), and toluene (5mL) were added to a pressure-resistant reaction flask, oxygen was removed by three freeze-pump-thaw cycles under nitrogen, and the reaction mixture was heated to 120 ℃ for polymerization for 18 hours. After cooling, the mixture was poured into 100mL of methanol, stirred at room temperature for 3 hours, and filtered. The obtained precipitate is loaded into a Soxhlet extractor for extraction. Firstly, methanol, acetone and normal hexane are used for extraction until the mixture is colorless, micromolecules and catalysts are removed, and then chloroform is used for extraction to obtain a final product 113.2mg with the yield of 81%.
The structural characterization data is as follows:
molecular weight: GPC Mn=20.0kDa,Mw=42.3kDa,PDI=2.1。
Elemental analysis: anal, calcd, for C78H96F2N2O2S4:C 72.34,H 8.79;found:C 72.16,H8.65.
As can be seen from the above, the polymer has a correct structure and is a polymer IID-CF represented by the formula I-13TVT, wherein R is 4-decyl tetradecyl, and n is a natural number of 18-40.
Example 3, formula I-2The polymer F-IID-CF3Preparation of TVT
Difluorocycloindigo-dibromo (as shown in formula III-2, R is 4-decyltetradecyl) (113mg,0.1mmol), 3-trifluoromethyl-2 (2- (3-trifluoromethyl-2-thienylethylene) vinylthiophene) (32.8mg,0.1mmol), Herrmann's catalyst (2.4mg,0.002mmol), the ligand tris (o-tolyl) phosphine (1.4mg,0.004mmol), pivalic acid (10.2 mg,0.1mmol), cesium carbonate (98mg,0.3mmol), and toluene (5mL) were added to a pressure-resistant reaction flask, deoxygenated under nitrogen for three freeze-pump-thaw cycles, and the reaction mixture was heated to 120 ℃ for polymerization for 18 hours. After cooling, the mixture was poured into 100mL of methanol, stirred at room temperature for 3 hours, and filtered. The obtained precipitate is loaded into a Soxhlet extractor for extraction. Firstly, methanol, acetone and normal hexane are used for extraction until the mixture is colorless, micromolecules and catalysts are removed, and then chloroform is used for extraction to obtain a final product of 110.5mg, wherein the yield is 76%.
The structural characterization data is as follows:
molecular weight: GPC Mn=15.7kDa,Mw=20.5kDa,PDI=1.3。
Elemental analysis: anal, calcd, for C78H96F2N2O2S4:C,70.34;H,8.39.Found(%):C,70.22;H, 8.41.
As can be seen from the above, the polymer has a correct structure and is a polymer F-IID-CF represented by the formula I-23TVT, wherein R is 4-decyl tetradecyl, and n is a natural number of 13-20.
Following the procedures of examples 2 and 3, using as the acceptor a compound of formula III-3-III-6, respectively, with CF of formula II3And polymerizing the TVT donor to obtain the polymer containing the trifluoromethyl thiophene ethylene thiophene donor.
Example 4 Polymer IID-CF3TVT and F-IID-CF3Spectral, electrochemical and field effect transistor performance of TVT
1) Polymer IID-CF3TVT and F-IID-CF3Spectral and electrochemical Properties of TVT
FIG. 1 shows a polymer IID-CF3TVT and F-IID-CF3Uv-vis absorption spectra of TVT in solution and thin films.
As can be seen from FIG. 1, the polymer IID-CF3TVT and F-IID-CF3The optical bandgaps of TVT are 1.67eV and 1.61eV, respectively (optical bandgaps according to equation E)g1240/λ calculation, where EgIs the optical band gap, and λ is the boundary value of the ultraviolet absorption curve). As can be seen from FIG. 1, both polymers have a relatively strong intramolecular charge transfer peak, indicating that the polymer has a strong intermolecular force.
The spectra of the polymers prepared from the compounds of the formulae III-3 to III-6 as acceptors were also determined, and the results showed that each polymer also had a relatively strong intramolecular charge transfer peak.
FIG. 2 is a drawing of polymer IID-CF3TVT and F-IID-CF3Cyclic voltammogram of TVT films.
The measurements were performed at the electrochemical workstation CHI660c and tested using a conventional three-electrode configuration with platinum as the working electrode, platinum wire as the counter electrode, silver/silver chloride as the reference electrode, and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The test was performed in acetonitrile solution. The cyclic voltammetry conditions were: the scan range is-1.8 to 1.8 volts (vs. Ag/AgCl) and the scan rate is 50 millivolts per second. Both polymers have oxidation peaks and reduction peaks and can be used as organic semiconductor materials. According to cyclic voltammograms, polymers IID-CF3TVT and F-IID-CF3The HOMO levels of the TVT are-6.02 eV and-6.11 eV, respectively, and the LUMO levels are-3.88 eV and-4.08 eV, respectively. The above indicates that the polymer has a lower HOMO level and a suitable LUMO level and is therefore a single n-type material.
And the cyclic voltammetry curves of the polymers prepared by using the compounds shown in the formulas III-3-III-6 as acceptors are simultaneously measured, and the results show that each polymer has a lower HOMO energy level and a proper LUMO energy level, so that the polymer is a single n-type material.
2) Polymer IID-CF3TVT and F-IID-CF3Field effect transistor performance of TVT
Fig. 3 is a schematic structural diagram of an organic field effect transistor, and as shown in the figure, a silicon wafer with a 300nm silicon dioxide layer is used as a substrate, silicon is used as a gate electrode, gold is used as a source and drain anode electrode, OTS (octadecyltrichlorosilane) modified silicon dioxide is used as an insulating layer, the polymers obtained in examples 1 to 2 are used as a semiconductor layer, a xylene solution with the concentration of 5mg/ml is used as a charge transport layer on the silicon wafer substrate by a glue spreading method, annealing is carried out on a hot stage at 200 ℃ for 10 minutes, and then 30 nm-thick gold is thermally evaporated by a vacuum evaporation method and used as a source and drain electrode, so that the preparation of the organic field effect transistor device is completed.
The electrical properties of the field effect devices prepared were measured at room temperature with a Keithley 4200SCS semiconductor tester. Two key parameters that determine the performance of OFETs are: carrier mobility (μ) and on-off ratio (I) of the deviceon/Ioff). The mobility refers to the average drift velocity of a carrier (unit is cm) under the action of a unit electric field2V-1s-1) Which reflects the mobility of holes or electrons in a semiconductor under an electric field. The on-off ratio is defined as: the ratio of the current in the "on" state and the "off" state of the transistor reflects the performance of the device switch. For a high performance field effect transistor, the mobility and switching ratio should be as high as possible.
FIG. 4 is a graph based on IID-CF3TVT and F-IID-CF3Transfer characteristic curve and output characteristic curve of field effect transistor prepared from TVT polymer. Two polymer field effect transistors exhibit a single n-type transfer characteristic.
The carrier mobility can be calculated from the equation:
IDS=(W/2L)Ciμ(VG–VT)2(saturation region)
Wherein, IDSIs the drain current, μ is the carrier mobility, VGIs the gate voltage, VTIs the threshold voltage, W is the channel width, L is the channel length, CiIs an insulator capacitor. Utilizing (I)DS,sat)1/2To VGPlotting, and performing linear regression to obtain carrier mobility (μ) from the slope of the regression line, and determining V from the intercept of the regression line and the X-axisT。
The mobility can be calculated from the slope of the transfer curve according to the formula, and the device properties of the polymer field effect transistor prepared in each of the above examples are shown in table 1. The switching ratio can be derived from the ratio of the maximum value to the minimum value of the side source-drain current in fig. 4.
Experimental results show that the trifluoromethyl substituted thiophene ethylene thiophene donor polymer is an excellent novel single n-type material.
The transfer characteristic curve and the output characteristic curve of the field effect transistor prepared based on the polymer prepared from the compound represented by the formula III-3-formula III-6 as an acceptor were simultaneously measured, and the results showed that each of the polymer field effect transistors exhibited a single n-type transmission characteristic.
The invention is not limited to the recorded materials, a series of polymers can be obtained by changing different acceptor units, and the synthesis method provided by the invention is simple and effective, and has great guiding significance for synthesizing new single n-type materials.
TABLE 1 device Performance of the Polymer field Effect transistor
Claims (9)
2. a preparation method of a compound shown as a formula II comprises the following steps:
1) taking ruthenium terpyridyl hexahydrate and cuprous acetate as catalysts, taking potassium carbonate as alkali, and reacting 2-formaldehyde thiophene-3-boric acid with trifluoroiodomethane under the excitation of blue visible light to obtain 2-formaldehyde thiophene-3-trifluoromethyl shown in a formula II-a;
2) under the catalysis of titanium tetrachloride or tetrahydrofuran titanium chloride and in the presence of zinc powder, 2-formaldehyde thiophene-3-trifluoromethyl shown in a formula II-a is reacted to obtain trifluoromethyl thiophene ethylene thiophene shown in a formula II in claim 1.
5. A process for the preparation of a polymer as claimed in claim 3 or 4, comprising the steps of:
carrying out polymerization reaction on a compound shown in a formula II and receptor monomers under the action of a catalyst and a ligand to obtain a polymer shown in a formula I according to claim 3 or 4;
the acceptor monomer is selected from any one of the following compounds:
6. the method of claim 5, wherein: the catalyst is selected from at least one of Herrmann's catalyst, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium;
the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine and triphenylarsine.
7. The production method according to claim 5 or 6, characterized in that: the molar ratio of the compound shown in the formula II, the receptor monomer, the catalyst and the ligand is 1: 1: 0.01-0.10: 0.04 to 0.80;
the temperature of the polymerization reaction is 90-140 ℃, and the time is 1 minute-24 hours.
The solvent for the polymerization reaction is at least one selected from the group consisting of toluene, chlorobenzene, and xylene.
8. Use of a polymer according to claim 3 or 4 for the preparation of an organic effect transistor.
9. An organic field effect transistor, characterized by: the material of the semiconductor layer of the organic field effect transistor is the polymer according to claim 3 or 4.
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