CN106750193A - Even tripyrrole and pyrroledione polymer and its synthetic method and application - Google Patents
Even tripyrrole and pyrroledione polymer and its synthetic method and application Download PDFInfo
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- CN106750193A CN106750193A CN201611138353.3A CN201611138353A CN106750193A CN 106750193 A CN106750193 A CN 106750193A CN 201611138353 A CN201611138353 A CN 201611138353A CN 106750193 A CN106750193 A CN 106750193A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- WIFCKLPZYYALGY-UHFFFAOYSA-N 1h-pyrrole-2,3-dione Chemical compound O=C1NC=CC1=O WIFCKLPZYYALGY-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 230000005669 field effect Effects 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 palladium chlorides Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 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 8
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical class [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [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
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 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
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 210000003746 feather Anatomy 0.000 description 7
- 244000144992 flock Species 0.000 description 7
- 125000001544 thienyl group Chemical group 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- YKPJEYXZEBLYCI-UHFFFAOYSA-N pyrrolo[3,4-c]pyrrole Chemical class C1=NC=C2C=NC=C21 YKPJEYXZEBLYCI-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 5
- 235000011167 hydrochloric acid Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MLCPSWPIYHDOKG-BUHFOSPRSA-N (3e)-3-(2-oxo-1h-indol-3-ylidene)-1h-indol-2-one Chemical compound O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RVPDWHCUEOPEGM-UHFFFAOYSA-N 6-thiophen-2-ylpyrrolo[3,4-c]pyrrole Chemical class S1C(=CC=C1)C1=NC=C2C1=CN=C2 RVPDWHCUEOPEGM-UHFFFAOYSA-N 0.000 description 4
- 241000271566 Aves Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000000950 dibromo group Chemical group Br* 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QUTGXAIWZAMYEM-UHFFFAOYSA-N 2-cyclopentyloxyethanamine Chemical compound NCCOC1CCCC1 QUTGXAIWZAMYEM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- LECHJHHAZKSBIL-UHFFFAOYSA-J N,N-dimethylmethanamine tetrachlorostannane Chemical compound [Sn](Cl)(Cl)(Cl)Cl.CN(C)C LECHJHHAZKSBIL-UHFFFAOYSA-J 0.000 description 1
- GZZMPRDPYFYDLW-UHFFFAOYSA-M O1CCCC1.C[Sn](C)(C)Cl Chemical compound O1CCCC1.C[Sn](C)(C)Cl GZZMPRDPYFYDLW-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G61/124—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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- H—ELECTRICITY
- 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]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/151—Copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—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 one kind even tripyrrole and pyrroledione polymer and its synthetic method and application.The structure of the polymer as shown in formula I, wherein, R is C1~C60Straight or branched alkyl.Present invention also offers the preparation method of polymer shown in Formulas I.Raw material of the invention is commercially produced product；Synthetic route is simple；Yield is high.Hole mobility with the even organic field effect tube that tripyrrole and pyrroledione polymer are prepared as organic semiconductor layer of the invention is up to 1.12cm2V‑1s‑1, electron mobility is up to 1.27cm2V‑1s‑1, there is good application prospect in organic field effect tube device.
Description
Technical field
The invention belongs to Material Field, be related to a kind of even tripyrrole and pyrroledione polymer and its synthetic method with should
With.
Background technology
Organic field effect tube (Organic field-effect transistors, abbreviation OFETs) is a kind of electricity
Pressure controller part, it regulates and controls source-electric leakage interpolar size of current by grid voltage, and organic semiconductor active layer is the core of the device
Center portion point.Its semiconductor layer can select organic conjugate small molecule and conjugated polymer.With inorganic field effect transistor (semiconductor
Layer is inorganic matter, such as monocrystalline silicon) to compare, organic field effect tube has device preparation technology simple, can large area solwution method
Printing processing, the advantages of flexible device can be prepared.Therefore, organic field effect tube receives the extensive concern of people, by the phase
Prestige can be applied to various display devices and memory aspect, such as electronic trademark, sensor, memory, large-scale integrated
Circuit and Active Matrix Display etc..Organic field effect tube is expected to take as the essential elements device of organic photoelectric circuit
For traditional inorganic field effect transistor device, brand-new business opportunities will be brought.
The semiconductor layer material played a crucial role in OFETs devices can be divided into p-type, N-shaped by its carrier transmission characteristics
With bipolar semiconductor material, its carrier is respectively hole, electronics, hole and electronics.Current research shows there are three individualities
The polymeric material of system shows excellent OFETs performances, and they are respectively pyrrolo-pyrrole-dione
(diketopyrrolopyrrole, abbreviation DPP), isoindigo green grass or young crops (Isoindigo, abbreviation IID) and naphthalimide
(Naphthalenedicarboximide, abbreviation NDI).In this three classes material, NDI classes material typically shows N-shaped performance,
And DPP and IID classes material typically shows p-type performance, this three classes material can show bipolarity performance in a few cases.
{X.Guo.；A.Facchetti.；T.J.Marks.Chem.Rev.2014,114,8943 } because bipolar materials are in CMOS
There is important purposes in (complementary metal-oxide-semiconductor) device, therefore synthesize new bipolar
Property material is extremely urgent.For DPP class materials, because the electron-withdrawing power of DPP cores is not strong, the lumo energy of its polymer compared with
Height, is unfavorable for electron injection and the transmission of transport layer, therefore such polymer is usually p-type material.
The content of the invention
It is an object of the invention to provide one kind even tripyrrole and pyrroledione polymer and its synthetic method and application.
Company's tripyrrole and pyrroledione polymer that the present invention is provided, namely 3DPP birds of the same feather flock together compound, its general structure such as Formulas I
It is shown：
In the Formulas I, R is that the total number of carbon atoms is the straight or branched alkyl of 1-60, and concretely the total number of carbon atoms is 1-
30th, the straight or branched alkyl of 10-30 or 20-30, more specifically can be 2- decyl myristyls, namely-CH2-CH(C10H21)
C12H25。
Ar groups are selected from any one in following group：
In the Ar groups,Represent substitution position；
N is 5-100, specifically, n is 8 or 11.
Polymer shown in the Formulas I is specially polymer P 3DPP-BT and P3DPP-TT；
Wherein, the P3DPP-BT structural formulas of the polymer are as follows：
The P3DPP-TT structural formulas of the polymer are as follows：
The method of polymer, comprises the following steps shown in the formula I that the present invention is provided：
Compound shown in Formula V (3DPP-2Br) is polymerized with double methyl tin compounds under catalyst and part effect
Reaction, obtains polymer shown in the Formulas I；
The definition of R is identical with the definition of R in previously described formula I.
In the above method, double methyl tin compounds are selected from any one in following compound：
(i.e. 5,5 '-bis- (tin trimethyls) -2,2 '-di- thiophene),
(i.e. double (tin trimethyl) thieno [3,2-b] thiophene of 2,5-)
The catalyst is selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides and three (dibenzalacetones) two
At least one in palladium；
The part is selected from least one in triphenylphosphine, three (o-tolyl) phosphines and triphenylarsine.
The molfraction that feeds intake of compound (3DPP-2Br) shown in the Formula V is for 1.00 parts；
The described pair of molfraction that feeds intake of methyl tin compound is for 0.95~1.05 part；
The molfraction that feeds intake of the catalyst is for 0.01~0.10 part；
The molfraction that feeds intake of the part is for 0.08~0.80 part；
The mole dosage that feeds intake of compound (3DPP-2Br) shown in the Formula V, double methyl tin compounds, catalyst and part
Than being specially 1.0：1.0：0.04：0.32；
In the polymerization procedure, temperature be 90~140, DEG C be specially 120 DEG C；
Polymerization time is 2 hours~80 hours；
The solvent of the polymerisation is chosen in particular from least one in toluene, chlorobenzene and dimethylbenzene.
Methods described may also include following purification step：
After the polymerisation is finished, concentrated hydrochloric acid and methyl alcohol are sequentially added after gained reaction system is cooled down, at room temperature
Agitation and filtration, gained precipitation is extracted with methyl alcohol, acetone, n-hexane successively with apparatus,Soxhlet's, and extracting is removed small to after colourless
Molecule and catalyst, then extracted with chloroform and obtained；Wherein, the volume ratio of methyl alcohol and hydrochloric acid concretely 20：1, hydrochloric acid
Concentration concretely 12M.
Additionally, compound shown in initiation material Formula V described above falls within protection scope of the present invention.
The definition of R is identical with the definition of R in Formulas I.
Compound shown in above-mentioned Formula V can in accordance with the following steps prepare gained：
1) excessive 2,5- dialkyl group -3,6- two (thienyl) pyrrolo- [3,4-c] pyrroles -1,4- diketone and N- bromo fourths
Imidodicarbonic diamide reacts in chloroform soln, obtains 3- (5- bromothiophene -2- bases) -2, the 5- dialkyl group -6- (thiophenes shown in Formula II
Fen -2- bases) pyrrolo- [3,4-c] pyrroles's -1,4- diketone；
The definition of R is identical with the definition of R in Formulas I.
2) 2,5- dialkyl group -3,6- two (thienyl) pyrrolo- [3,4-c] pyrroles -1,4- diketone and excessive diisopropyl
Lithium amide and trimethyltin chloride react in tetrahydrofuran solution, obtain 2,5- dialkyl group -3 shown in the formula III, (5- of 6- bis-
(trimethyl-tin-radical) thienyl) pyrrolo- [3,4-c] pyrroles's -1,4- diketone；
The definition of R is identical with the definition of R in Formulas I.
3) by step 1) gained Formula II shown in 3- (5- bromothiophene -2- bases) -2,5- dialkyl group -6- (thiophene -2- bases) pyrrole
Cough up simultaneously [3,4-c] pyrroles -1,4- diketone and step 2) gained formula III shown in (5- (the tin trimethyls of 2,5- dialkyl group -3,6- two
Base) thienyl) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone carries out coupling reaction under tetrakis triphenylphosphine palladium catalytic action, obtains
To connecting tripyrrole and pyrroledione (i.e. 3DPP) shown in formula IV；
The definition of R is identical with the definition of R in Formulas I.
4) by step 3) connect tripyrrole and pyrroledione (i.e. 3DPP) shown in gained formula IV and exist with N- bromo-succinimides
Reacted in chloroform soln, obtain the dibromo shown in Formula V and connect tripyrrole and pyrroledione (i.e. 3DPP-2Br).
Above method step 1) in, 2,5- dialkyl group -3,6- bis- (thienyl) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae -
Diketone is 1.5 with the mole dosage ratio that feeds intake of N- bromo-succinimides：1.0~1.5, preferably 1.5：1；In reactions steps, temperature
It is -10~25 DEG C to spend, and the time is 2~24 hours；
Above-mentioned steps 2) in, 2,5- dialkyl group -3,6- bis- (thienyl) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone
Mole dosage ratio is fed intake for 1 with lithium diisopropylamine and trimethyltin chloride：2.0~3.0：2.0~4.0, preferably 1：2.5：
3；In reactions steps, temperature is -80~0 DEG C, and the time is 1~24 hour；
Above-mentioned steps 3) in, 3- (5- bromothiophene -2- bases) -2,5- dialkyl group -6- (thiophene -2- bases) pyrrolo- [3,
4-c] pyrroles -1,4- diketone, 2,5- dialkyl group -3,6- two (5- (trimethyl-tin-radical) thienyl) pyrrolo- [3,4-c] pyrroles -1,
The mole dosage ratio that feeds intake of 4- diketone and tetrakis triphenylphosphine palladium is 1：2.0~4.0：0.01~0.2, preferably 1：2.5：0.1；Instead
Answer in step, temperature is 80~140 DEG C, the time is 2~48 hours；
Above-mentioned steps 4) in, simultaneously pyrroledione (i.e. 3DPP) rubs the even tripyrrole with feeding intake for N- bromo-succinimides
Your amount ratio is 1:2.0~2.5, preferably 1：2.2；In reactions steps, temperature is -10~25 DEG C, and the time is 2~24 hours；
Above-mentioned steps 1) to step 4) reaction carries out in organic solvent.The step 1) in, the solvent tool
Body can be chloroform；The step 2) in, the solvent concretely tetrahydrofuran；The step 3) in, the solvent tool
Body may be selected from least one in toluene, chlorobenzene and dimethylbenzene；The step 4) in, the solvent concretely chloroform.
The synthetic route of the above method is as shown in Figure 5.
Application of the compound in organic field effect tube is prepared shown in the Formulas I that the invention described above is provided and containing described
The organic field effect tube of polymer shown in Formulas I, falls within protection scope of the present invention.The organic field effect tube
In, the material for constituting semiconductor layer is polymer shown in any Formulas I of claim 1 or 2.
The advantage of the invention is that：
1st, raw material is commercially produced product, and synthetic route is simple, and yield is high, can also be generalized to various straight or branched 3DPP
Birds of the same feather flock together the synthesis of compound；
2nd, 3DPP birds of the same feather flock together compound symmetry and flatness it is all fine, birdsed of the same feather flock together compound compared to DPP, 3DPP birdss of the same feather flock together compound electrophilic
Ability is stronger, with lower lumo energy, is conducive to the injection and transmission of semiconductor layer electronics, can be used for bipolarity field-effect
In transistor；
3rd, 3DPP compounds of birdsing of the same feather flock together have suitable energy level and band gap, can be used in the photoelectric devices such as organic solar batteries；
4. mobility higher is had with 3DPP of the present invention organic field effect tubes that compound prepared as semiconductor layer of birdsing of the same feather flock together
(μ) (hole mobility is up to 1.12cm2V-1s-1；Electron mobility is up to 1.27cm2V-1s-1), in bipolarity OFETs
There is good application prospect.
Brief description of the drawings
Fig. 1 is the company's tripyrrole provided with the present invention and the ultraviolet-visible absorption spectroscopy figure of pyrroledione polymer.
Fig. 2 is the company's tripyrrole provided with the present invention and the cyclic voltammetry curve figure of pyrroledione polymer.
Fig. 3 is the company's tripyrrole provided with the present invention and the structural representation of pyrroledione polymer field effect transistor.
Fig. 4 is brilliant for the polymer field-effect of the company's tripyrrole and pyrroledione polymer as semiconductor layer that are provided with the present invention
The output characteristic curve figure and transfer characteristic curve figure (P3DPP-BT and P3DPP-TT) of body pipe.
The synthetic route of compound shown in the formula I that Fig. 5 is provided for the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
State method and be conventional method unless otherwise instructed.The raw material can be obtained from open commercial sources unless otherwise instructed.
Embodiment 1, polymer P 3DPP-BT
1) 3- (5- bromothiophene -2- bases) -2,5- two (2- decyls myristyl) -6- (thiophene -2- bases) pyrrolo- [3,4-c]
Pyrroles's -1,4- diketone
N- bromo-succinimides (0.64g, 3.59mmol) are dividedly in some parts (the 2- decyls 14 of 2,5- bis- under ice bath
Alkyl) -3,6- two (thienyl) pyrrolo- [3,4-c] pyrroles -1,4- diketone (5.25g, 5.39mmol) chloroform
In (30mL) solution, after stirring 20min, ice bath is removed, 6h is reacted at room temperature.Extracted with water and dichloromethane, dried.Solution revolves
Post is crossed after dry, and (eluant, eluent is petroleum ether：Dichloromethane=8:1) red solid 2.6g, is obtained.Yield：68.9%.
Structural characterization data are as follows：
Mass spectrum：HR-MALDI-TOF:[M+Na]+calcd for C62H103BrN2NaO2S2:1073.654234,found:
1073.654192.
Nucleus magnetic hydrogen spectrum and carbon are composed：1H NMR(400MHz,CDCl3) δ 8.88 (d, J=4.0Hz, 1H), 8.61 (d, J=
4.0Hz, 1H), 7.63 (d, J=4.0Hz, 1H), 7.28 (m, 1H), 7.21 (d, J=4.0Hz, 1H), 4.05-3.90 (dd, J1
=7.8Hz, J2=7.8Hz, 4H), 1.88 (br, 2H), 1.44-1.05 (m, 80H), 0.88 (m, 12H)13C NMR(100MHz,
CDCl3)δ161.84,161.67,141.08,140.10,135.71,135.26,131.54,131.44,130.99,129.94,
118.92,108.48,107.41,46.46,37.96,37.92,32.13,31.35,30.21,29.91,29.89,29.87,
29.85,29.76,29.58,26.38,22.91,14.34.
2) 2,5- bis- (2- decyls myristyl) -3,6- two (5- (trimethyl-tin-radical) thienyl) pyrrolo- [3,4-c] pyrrole
Cough up -1,4- diketone
By 2,5- bis- (2- decyls myristyl) -3,6- two (thienyl) pyrrolo- [3,4-c] pyrroles's -1,4- diketone
(1.0g, 1.027mmol) is dissolved in anhydrous THF (20mL), is cooled to -20 DEG C, and lithium diisopropylamine solution is dropwise added dropwise
(2M, 1.28mL, 2.57mmol), reaction 30min after, add trimethyltin chloride tetrahydrofuran solution (1M, 3.08mL,
3.08mmol), 8h is reacted.Water quenching is added dropwise to go out reaction, dichloromethane is extracted, saturation potassium fluoride solution washes away excessive trimethyl ammonia chloride
Tin.Organic phase anhydrous sodium sulfate drying, is spin-dried for.Product dichloromethane and acetone mixture freezing and crystallizing.After freeze overnight,
Filter to obtain solid 0.62g.Yield：46.5%.
Structural characterization data are as follows：
Mass spectrum：HR-MALDI-TOF:[M+H]+calcd for C68H121N2O2S2Sn2:1299.690936,found:
1299.692355.
Nucleus magnetic hydrogen spectrum and carbon are composed：1H NMR(400MHz,CDCl3) δ 8.97 (d, J=3.6Hz, 2H), 7.31 (d, J=
3.6Hz, 2H), 4.03 (d, J=7.5Hz, 4H), 1.90 (m, 2H), 1.24 (m, 80H), 0.87 (t, 12H), 0.44 (s, 18H)
.13C NMR(100MHz,CDCl3)δ162.06,146.48,140.10,136.41,136.12,135.83,107.65,46.44,
38.40,32.41,31.84,30.52,30.43,30.12,30.07,29.82,26.85,23.15,14.36,-7.96.
3) tripyrrole and pyrroledione (i.e. 3DPP) are connected
To in bis- mouthfuls of bottles of 100mL add 3- (5- bromothiophene -2- bases) -2,5- two (2- decyls myristyl) -6- (thiophene -
2- yls) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone (1.01g, 0.962mmol), 2,5- bis- (2- decyls myristyls) -3,6-
Two (5- (trimethyl-tin-radical) thienyl) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone (0.50g, 0.385mmol), four (triphenyls
Phosphine) palladium (44.5mg, 0.0385mmol), leads to argon gas protection.The toluene that 20mL ultrasounds are crossed is subsequently added into, mixed liquor is under 110 degree
Reaction 24h.Room temperature is cooled to, water and dichloromethane extraction is added, dried.Solution crosses post after being spin-dried for, and (eluant, eluent is petroleum ether：Two
Chloromethanes=1:1) blue solid 0.59g, is obtained.Yield：52.8%.
Structural characterization data are as follows：
Mass spectrum：HR-MALDI-TOF:[M+Na]+calcd forC186H308N6NaO6S6:2939.226981,found:
2939.224302。
Nucleus magnetic hydrogen spectrum and carbon are composed：1H NMR(400MHz,CD2Cl2) δ 9.03 (d, 2H), 8.96 (d, J=4.2Hz, 2H),
8.89 (d, 2H), 7.59 (d, J=4.2Hz, 2H), 7.36 (d, J=3.9Hz, 4H), 7.22 (t, 2H), 3.99 (d, J=
7.5Hz,12H),1.94(m,6H),1.30–1.18(m,240H),0.86(m,36H).13C NMR(100MHz,CDCl3)δ
160.54,160.52,160.43,140.16,139.80,139.46,138.11,138.02,135.96,135.63,134.51,
129.63,128.82,128.80,128.65,127.41,124.90,108.11,107.87,107.19,45.43,45.35,
37.08,36.79,30.92,30.30,30.24,29.11,29.04,28.70,28.66,28.64,28.57,28.37,
25.32,25.25,21.84,21.68,21.50,13.08,12.90.
4) dibromo connects tripyrrole and pyrroledione (i.e. 3DPP-2Br)
By N- bromo-succinimides (67.1mg, the 0.377mmol) company's of being dividedly in some parts tripyrrole and pyrroles under ice bath
In chloroform (10mL) solution of diketone (i.e. 3DPP) (0.50g, 0.17mmol), after stirring 20min, ice bath, room temperature are removed
Lower reaction 6h.Water and dichloromethane extraction are added, is dried.Solution crosses post after being spin-dried for, and (eluant, eluent is petroleum ether：Dichloromethane=1:
1) blue solid 0.32g, is obtained.Yield：61.3%.
Structural characterization data are as follows：
Mass spectrum：HR-MALDI-TOF:[M+Na]+calcd for C124H204Br2N4NaO4S4:3096.042603,found:
3096.045214。
Nucleus magnetic hydrogen spectrum and carbon are composed：1H NMR(400MHz,CDCl3) δ 8.94 (m, 4H), 8.63 (d, J=4.0Hz, 2H),
7.39 (d, J=4.0Hz, 4H), 7.19 (d, J=4.0Hz, 2H), 4.01 (m, 12H), 1.91 (m, 6H), 1.28-1.00 (m,
240H),0.85(m,36H).13C NMR(100MHz,CDCl3)δ160.99,160.91,141.38,138.88,138.67,
138.57,136.65,135.31,131.27,131.07,129.84,129.76,125.58,118.93,108.81,108.33,
108.02,53.29,46.35,37.95,37.87,37.72,31.92,31.32,30.12,30.07,29.70,29.64,
29.37,26.40,26.31,22.67,14.06.
5) polymer P 3DPP-BT
Dibromo is connected into tripyrrole and pyrroledione (i.e. 3DPP-2Br) (100.0mg, 0.0325mmol), 5,5 '-bis- (front threes
Ji Xi) -2,2 '-di- thiophene (16.0mg, 0.0325mmol), the palladium of catalyst three (dibenzalacetone) two (1.2mg,
0.0013mmol), part three (o-tolyl) phosphine (3.17mg, 0.0104mmol) and chlorobenzene (3mL) are added in reaction bulb,
The deoxygenation of three freezing-pumping-thaw cycles is carried out in argon gas, reactant mixture then is heated into 120 DEG C carries out polymerisation
72h.After cooling, add 5mL 12mol/L concentrated hydrochloric acids, 100mL methyl alcohol to stir 3h at room temperature, filter.The sediment for obtaining loads
Apparatus,Soxhlet's is extracted.First extracted to colourless with methyl alcohol, acetone, n-hexane, remove small molecule and catalyst, then use chloroform
Extracting obtains final product 84mg, yield 83.9%.
Structural characterization data are as follows：
Molecular weight：GPC:Mn=27.0kDa, PDI=2.65, n=8.
Elementary analysis：Anal.calcd for C194H310N6O6S8:C 75.68,H 10.22,N 2.73,found:C
75.74,H 10.25,N 2.68。
From the foregoing, it will be observed that the compound structure is correct, and it is compound P3DPP-BT shown in Formulas I, structural formula is as follows：
Embodiment 2, polymer P 3DPP-TT
Dibromo is connected into tripyrrole and the double (front threes of pyrroledione (i.e. 3DPP-2Br) (100.0mg, 0.0325mmol), 2,5-
Ji Xi) thieno [3,2-b] thiophene (15.1mg, 0.0325mmol), the palladium of catalyst three (dibenzalacetone) two (1.2mg,
0.0013mmol), part three (o-tolyl) phosphine (3.17mg, 0.0104mmol) and chlorobenzene (3mL) are added in reaction bulb,
The deoxygenation of three freezing-pumping-thaw cycles is carried out in argon gas, reactant mixture then is heated into 120 DEG C carries out polymerisation
72h.After cooling, add 5mL 12mol/L concentrated hydrochloric acids, 100mL methyl alcohol to stir 3h at room temperature, filter.The sediment for obtaining loads
Apparatus,Soxhlet's is extracted.First extracted to colourless with methyl alcohol, acetone, n-hexane, remove small molecule and catalyst, then use chloroform
Extracting obtains final product 88mg, yield 88.6%.
Structural characterization data are as follows：
Molecular weight：GPC:Mn=33.6kDa, PDI=2.45, n=11.
Elementary analysis：Anal.calcd for C192H308N6O6S8:C 75.53,H 10.17,N 2.75,found:C
75.54,H 10.20,N 2.68。
From the foregoing, it will be observed that the compound structure is correct, and it is compound P3DPP-TT shown in Formulas I, structural formula is as follows：
Embodiment 3, the spectrum property of polymer P 3DPP-BT and P3DPP-TT, chemical property and field-effect transistor
Energy
1) spectrum and chemical property of polymer P 3DPP-BT and P3DPP-TT
Fig. 1 is ultraviolet-visible absorption spectroscopy of the two kinds of polymer in solution and film.
As shown in Figure 1, the optical band gap of polymer P 3DPP-BT and P3DPP-TT films is respectively 1.27eV and 1.26eV
(optical band gap is according to formula Eg=1240/ λ is calculated, wherein EgIt is optical band gap, λ is the boundary value of ultraviolet absorption curve).By scheming
1 understands, the polymer all has stronger Intramolecular electron transfer peak, shows that the polymer molecule intermolecular forces are stronger.
Fig. 2 is the cyclic voltammetry curve of two kinds of polymer film.Measure is carried out in CHI660c electrochemical workstations, with biography
The three-electrode structure test of system, platinum is working electrode, and platinum filament is that, to electrode, silver/silver chlorate is reference electrode, tetrabutyl hexafluoro phosphorus
Sour ammonium is used as supporting electrolyte.Test is carried out in acetonitrile solution.The condition of cyclic voltammetric is：Sweep limits is -1.6~1.6
Volt (vs.Ag/AgCl), sweep speed is 50 millivolts per second.The polymer has oxidation peak and reduction peak, can be used as organic half
Conductor material.According to cyclic voltammetry curve, the HOMO energy levels of polymer P 3DPP-BT and P3DPP-TT be respectively -5.45eV and -
5.44eV, lumo energy is respectively -3.51eV and -3.56eV.Polymer has suitable HOMO energy levels and lumo energy, thus
It is bipolar materials.
2) field-effect transistor performance of polymer P 3DPP-BT and P3DPP-TT
Fig. 3 is the structural representation of organic field effect tube, as illustrated, it is 200 μm of poly- terephthaldehydes to use thickness
Sour glycol ester piece is cleaned by ultrasonic after 80 DEG C of vacuum drying as substrate in secondary water, ethanol, acetone.Source-drain electrode is
The 25nm of mask plate hot evaporation thick Jin Weiyuan, drain electrode.The polymer of the gained of embodiment 1 is semiconductor layer, is by its concentration
Method in the o-dichlorobenzene solution of 8mg/ml by spin coating forms active layer in polyethylene terephthalate, and thickness is
20nm, and annealed 10 minutes in 160 DEG C of thermal station.
Then the polymeric film surface in the gained of 1~embodiment of embodiment 2 forms the poly- first of 900 nanometer thickness by spin coating
Used as FET insulating barrier, 90 DEG C are removed solvent 60 minutes to base methyl acrylate；Pass through mask plate hot evaporation on the insulating layer
50nm thickness aluminium completes FET and prepares as gate electrode.
At room temperature prepared fieldtron is measured with by the SCS semi-conductor test instruments of Keithley 4200
Electric property.Determining two key parameters of the performance of OFET is：The mobility (μ) and the on-off ratio (I of device of carrieron/
Ioff).Mobility refers to that (unit is cm to the average drift velocity of carrier under unit electric field effect2V-1s-1), it is reflected
Hole or electronics transfer ability in the semiconductors under the electric field.On-off ratio is defined as：Transistor is in "On" state and "Off" shape
The ratio between electric current under state, it reflects the quality of devices switch performance.For a high performance field-effect transistor, its migration
Rate and on-off ratio should be high as far as possible.
Fig. 4 is transfer characteristic curve and output characteristic curve based on the field-effect transistor prepared by two kinds of polymer.
The polymer field effect transistor shows obvious bipolar transmission characteristic, the company's of explanation tripyrrole and pyrroledione polymer
It is a class bipolar materials.
Carrier mobility can be calculated by equation：
IDS=(W/2L) Ciμ(VG–VT)2(saturation region)
Wherein, IDSIt is drain current, μ is carrier mobility, VGIt is grid voltage, VTIt is threshold voltage, W is that raceway groove is wide
Degree, L is channel length, CiIt is insulation body capacitance.Utilize (IDS, sat)1/2To VGMapping, and make linear regression, can thus return
The slope of line extrapolates carrier mobility (μ), and V is tried to achieve by the section of the tropic and X-axisT。
Mobility can be calculated according to formula from the slope of transfer curve, the polymer prepared in above-mentioned each example effect
Answer the device performance of transistor as shown in table 1.On-off ratio can be drawn by the ratio between maxima and minima of Fig. 4 sides source-drain current.
The device performance of table 1, polymer field effect transistor
Test result indicate that, the company's tripyrrole and pyrroledione polymer provided with the present invention are as prepared by organic semiconductor layer
The hole mobility of organic field effect tube be up to 1.12cm2V-1s-1, electron mobility is up to 1.27cm2V-1s-1。
It can be seen that, the company's tripyrrole and pyrroledione polymer that the present invention is provided are the excellent new bipolar materials of a class.The present invention
This material reported is not limited to, changing different side chain substituents can obtain a series of polymer, and the present invention
The synthetic method for being given is simple, effective, and the bipolar materials for synthesizing new have very big directive significance.
Claims (10)
1. polymer shown in Formulas I：
In the Formulas I, R is that the total number of carbon atoms is the straight or branched alkyl of 1-60；
Ar groups are selected from any one in following group；
In the Ar groups,Represent substitution position；
N is 5-100.
2. polymer according to claim 1, it is characterised in that：R is that the total number of carbon atoms is the straight chain of 1-30 in the Formulas I
Or branched alkyl or 2- decyl myristyls.
3. a kind of method for preparing polymer shown in any Formulas I of claim 1 or 2, comprises the following steps：
Compound shown in Formula V is carried out into polymerisation with double methyl tin compounds in the presence of catalyst and part, has been reacted
Polymer shown in the Formulas I is obtained after；
In the Formula V, the definition of R is identical with the definition of R in Formulas I in claim 1.
4. method according to claim 3, it is characterised in that：Described pair of methyl tin compound is selected from following compound
Any one：
The catalyst is selected from tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides and three (dibenzalacetone) two palladium
At least one；
The part is selected from least one in triphenylphosphine, three (o-tolyl) phosphines and triphenylarsine.
5. the method according to claim 3 or 4, it is characterised in that：The molfraction that feeds intake of compound shown in the Formula V is
1.00 parts；
The described pair of molfraction that feeds intake of methyl tin compound is for 0.95~1.05 part；
The molfraction that feeds intake of the catalyst is for 0.01~0.10 part；
The molfraction that feeds intake of the part is for 0.08~0.80 part.
6. according to any described method in claim 3-5, it is characterised in that：In the polymerization procedure, temperature is 90
~140 DEG C；Time is 2 hours~80 hours；
The polymerisation is carried out in a solvent；
The solvent of the polymerisation is chosen in particular from least one in toluene, chlorobenzene and dimethylbenzene.
7. application of the polymer in organic field effect tube is prepared shown in any Formulas I of claim 1 or 2.
8. the organic field effect tube of polymer shown in any Formulas I of claim 1 or 2 is contained.
9. it is according to claim 7 application or claim 8 described in organic field effect tube, it is characterised in that：Institute
State in organic field effect tube, the material for constituting semiconductor layer is polymer shown in any Formulas I of claim 1 or 2.
10. compound shown in Formula V,
In the Formula V, the definition of R is identical with the definition of R in Formulas I described in claim 1.
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| CN109734879A (en) * | 2019-01-09 | 2019-05-10 | 福州大学 | Two kinds contain isomers repetitive unit locally asymmetric conjugated polymer and preparation method thereof |
| CN110922418A (en) * | 2019-11-18 | 2020-03-27 | 河北工业大学 | Pyrrolo-pyrrole-dione conjugated oligomer, nanoparticle based on pyrrolo-pyrrole-dione conjugated oligomer and preparation methods of pyrrolo-pyrrole-dione conjugated oligomer and nanoparticle |
| CN114773580A (en) * | 2022-04-29 | 2022-07-22 | 太原理工大学 | Irregular ternary conjugated polymer photocatalytic material and preparation method and application thereof |
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| CN114773580A (en) * | 2022-04-29 | 2022-07-22 | 太原理工大学 | Irregular ternary conjugated polymer photocatalytic material and preparation method and application thereof |
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