CN104045817B - A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers and preparation method thereof and application - Google Patents
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers and preparation method thereof and application Download PDFInfo
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- CN104045817B CN104045817B CN201310079892.4A CN201310079892A CN104045817B CN 104045817 B CN104045817 B CN 104045817B CN 201310079892 A CN201310079892 A CN 201310079892A CN 104045817 B CN104045817 B CN 104045817B
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229920001577 copolymer Polymers 0.000 title claims abstract description 73
- 229930192474 thiophene Natural products 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 150000001356 alkyl thiols Chemical class 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 230000005669 field effect Effects 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 162
- 238000006243 chemical reaction Methods 0.000 claims description 162
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 96
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 62
- 239000000047 product Substances 0.000 claims description 49
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 37
- 238000004062 sedimentation Methods 0.000 claims description 36
- 238000000967 suction filtration Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 31
- 238000010025 steaming Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 9
- 229920006362 Teflon® Polymers 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005374 membrane filtration Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005401 electroluminescence Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 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
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000006619 Stille reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- LECHJHHAZKSBIL-UHFFFAOYSA-J N,N-dimethylmethanamine tetrachlorostannane Chemical compound [Sn](Cl)(Cl)(Cl)Cl.CN(C)C LECHJHHAZKSBIL-UHFFFAOYSA-J 0.000 claims 1
- 125000005605 benzo group Chemical group 0.000 abstract description 35
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical group C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 230000005587 bubbling Effects 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 239000003480 eluent Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 0 *C(S1)=C(*)SC1=C([C@@]1C=CSC11)c([s]cc2)c2C1=C1SC(*)=C(*)S1 Chemical compound *C(S1)=C(*)SC1=C([C@@]1C=CSC11)c([s]cc2)c2C1=C1SC(*)=C(*)S1 0.000 description 7
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical class BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 7
- 238000007445 Chromatographic isolation Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000011097 chromatography purification Methods 0.000 description 7
- 229920000547 conjugated polymer Polymers 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000002366 time-of-flight method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ANDMCHYYOUARBQ-SEYXRHQNSA-N C1NC=CN/C1=C(/c1c2[o]cc1)\c([nH]cc1)c1C2=C1NC=CN1 Chemical compound C1NC=CN/C1=C(/c1c2[o]cc1)\c([nH]cc1)c1C2=C1NC=CN1 ANDMCHYYOUARBQ-SEYXRHQNSA-N 0.000 description 1
- GOYKIDFYSVZFFU-LURJTMIESA-N C[C@@H]1CSC=CC1 Chemical compound C[C@@H]1CSC=CC1 GOYKIDFYSVZFFU-LURJTMIESA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 octadecyl trichlorosilane alkane Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004528 spin coating 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
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention provides a kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers and preparation method thereof and application, described is the compound P with following structural formula containing indone-two Thienopyrroles-benzo two thiophene copolymers,
wherein, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60.Described indone-two Thienopyrroles-benzo two thiophene copolymers that contains contains 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, two Thienopyrroles and indone unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, improve effciency of energy transfer, preparation method is simply controlled, has good application prospect in polymer solar battery, organic electroluminescent and organic field effect tube field.
Description
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers and preparation method thereof and application.
Background technology
The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point of photovoltaic art always.At present business-like silicon solar cell due to complex manufacturing, cost high, application is restricted.In order to reduce costs, expansive approach scope, people are finding novel solar cell material always for a long time.Polymer solar battery has superior market outlook because the mode big area such as low in raw material price, quality are light, flexibility, simple, the available coating of production technique, printing such as to prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.SSariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474) upper report conjugated polymers and C
60between Photo-induced electron transfer phenomenon after, people have dropped into large quantity research in polymer solar battery, and achieve development at full speed.
One of following facing challenges of polymer solar battery is exactly the P-type conjugated polymers of synthesizing new, and it needs to possess following characteristics: (a) good solubility, is conducive to solvent processing, realizes suitability for industrialized production; B () has wide and strong absorption to whole sunlight spectrum; C carrier mobility that () is high, is conducive to carrier transport.Wherein how to widen the light abstraction width of polymer materials, making its light abstraction width farthest cover whole sunlight spectrum will be the emphasis studied.
Summary of the invention
For solving the problem, the present invention aims to provide a kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, containing 4 in this multipolymer, 8-bis-(1, 3-bis-mercaptan-2-aldehyde) benzo [1, 2-b:4, 5-b '] two thiophene derivants, two Thienopyrroles unit and indone unit, by 4, 8-bis-(1, 3-bis-mercaptan-2-aldehyde) benzo [1, 2-b:4, 5-b '] two thiophene derivants and two Thienopyrroles donor monomer are as main polymer chain, and using indone class dyestuff as being articulated on side chain by body unit, by main chain and side chain to the interaction of this in acceptor " pushing away-La electronics ", add the two-dimentional conjugated system that master interchain is formed, reduce the energy gap of conjugated polymers simultaneously, substantially increase the light abstraction width of material.The present invention also aims to preparation method and application that above-mentioned indone-two Thienopyrroles-benzo two thiophene copolymers is provided.
First aspect, the invention provides a kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, for having the copolymer p of following structural formula:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60.
Benzo [1,2-b:4,5-b '] two thiophene are the up-and-coming electron donor(ED) unit of a class, and it is particularly extensively studied in the application in the fields such as organic electronic in organic polymer solar cell.Because benzo [1,2-b:4,5-b '] two thiophene-based monomers have good symmetry and planarity, the polymkeric substance therefore based on it has good carrier mobility.And 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants introduce 1,3-bis-mercaptan-2-aldehyde derivative 4,8 of benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone.1,3-bis-mercaptan-2-aldehyde derivative as the good electron donor material of a class, its introducing further enhance benzo [1,2-b:4,5-b '] two thiophene derivants to Electronic Performance.Therefore, the electronics itself had just because of 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and geometrical property, the application that it will expand in polymer solar battery as excellent donor monomer.
By 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and two Thienopyrroles donor monomer as main polymer chain, and using indone class dyestuff as being articulated on side chain by body unit, by main chain and side chain to the interaction of this in acceptor " pushing away-La electronics ", add and reduce the two-dimentional conjugated system that master interchain is formed the energy gap of conjugated polymers simultaneously, substantially increase the light abstraction width of material.
Second aspect, the invention provides a kind of preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers, comprises following operation steps:
(1) polymer B is prepared;
The compd A providing following structural formula to represent respectively and compound g:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched;
In atmosphere of inert gases, be that the compd A of 1:1 ~ 1.5:1 and compound g add in the first organic solvent and dissolve by mol ratio, then add catalyzer and form mixed solution, this mixed solution carries out Stille coupling reaction 24 ~ 72 hours at 60 ~ 120 DEG C, after stopped reaction, separation and purification obtains polymer B, and the structural formula of this polymer B is as follows:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60;
Reaction formula is:
(2) copolymer p is prepared;
Structural formula is provided
shown compound h:
Join in the second organic solvent by the polymer B of mol ratio 1:20 ~ 1:25 and compound h, drip pyridine, stirring reaction 20 ~ 24h under 30 ~ 40 DEG C of lucifuge conditions, after stopped reaction, separation and purification obtains copolymer p, and reaction formula is:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60.
Preferably, described catalyzer is the mixture of organic palladium or organic palladium and organic phosphine.
More preferably, described organic palladium is two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2) or tetrakis triphenylphosphine palladium (Pd (PPh
3)
4), the mixture of described organic palladium and organic phosphine is three (dibenzalacetone) two palladium (Pd
2(dba)
3) and three (2-tolyl) phosphine (P (o-Tol)
3) mixture; Pd in described organic palladium and organic phosphine mixture
2(dba)
3with P (o-Tol)
3mol ratio is 1:2 ~ 1:20.
Preferably, the mole dosage of described organic palladium is 0.01% ~ 5% of compound g mole dosage.
Preferably, described first organic solvent is tetrahydrofuran (THF), DMF or toluene.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described second organic solvent is chloroform.
Preferably, the ratio of described polymer B and pyridine is that 1mol polymer B needs 2.8 ~ 3L pyridine.
Preferably, step (1) described separation purification method is:
After the completion of reaction, by the underpressure distillation of polymer B reaction solution, remove the first excessive organic solvent, then be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, methanol wash, dry; Then by column chromatography, chloroform drip washing; Distillation removing organic solvent, methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction several, methyl alcohol sedimentation, suction filtration, is pumped through under vacuum pump and obtains product night.
Preferably, step (2) described separation purification method is:
The underpressure distillation of copolymer p reaction solution is removed the second excessive organic solvent, then pours in methyl alcohol, generate and precipitate in a large number, then filter, obtain crude product; After again crude product being dissolved with chloroform, through Teflon filtration membrane filtration after, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P night.
Preferably, described compd A can be prepared by following methods:
(1) compound a providing following structural formula to represent respectively and compound b:
R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched;
In atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound b is cooled to-78 DEG C, slowly add the cyclohexane solution of lithium diisopropyl amido (LDA), at-78 DEG C after stirring reaction 2 ~ 3h, then add the tetrahydrofuran solution of compound a, carry out Wittig-Horner reaction, room temperature is returned to after insulation reaction 0.5 ~ 1h, continue reaction 12 ~ 15h, obtain product after separation and purification, i.e. compound c; Wherein, the mol ratio of LDA and b is the mol ratio of 1:1 ~ 1.5:1, a and b is 1:2.0 ~ 1:2.5, and its reaction formula is as follows:
(2) in atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound c is cooled to-78 DEG C, slowly adds the hexane solution of n-Butyl Lithium (n-BuLi), then stirring reaction 2 ~ 3h at-78 DEG C, then add trimethyltin chloride (Me
3snCl) reagent, returns to room temperature after insulation reaction 0.5 ~ 1h, continues reaction 20 ~ 24h, obtains product, i.e. compd A; Wherein, the mol ratio of n-BuLi and c is 2.2:1 ~ 2.5:1, Me
3the mol ratio of SnCl and c is 2.0:1 ~ 2.5:1, and its reaction formula is as follows:
R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched;
Preferably, the separation purification method preparing compd A step (1) is: the reaction solution of compound c is through silica gel column chromatography separating purification, and eluent is normal hexane and methylene dichloride is obtain after 3:1 ~ 5:1 mixing by volume.
Preferably, in described inert atmosphere, gas is nitrogen or argon gas.
Preferably, described compound g can buy and obtain or prepare by the following method:
(1) magnesium rod, a small amount of iodine powder and 2 ~ 3 2-bromothiophenes are mixed to join in dry ether, under argon shield, heated and stirred to 40 DEG C backflow.Slowly be added dropwise to the diethyl ether solution of 2-bromothiophene again, after dropwising, at 40 DEG C, continue back flow reaction 1h, cool for subsequent use, obtain Verbindung; Then Verbindung is slowly added dropwise to containing compound d, catalyst P d (PPh
3)
2cl
2with in the reaction flask of tetrahydrofuran (THF), stir and back flow reaction 4h at being heated to 60 DEG C, stopped reaction is also cooled to room temperature.Reaction solution is poured into the saturated NH of 50mL
4in the Cl aqueous solution, after extraction into ethyl acetate, merge organic phase and use anhydrous Na
2sO
4dried overnight.Filter, revolve after steaming organic solvent, product f is obtained through silica gel column chromatography separating purification, wherein, the concentration of 2-bromothiophene in ether is 0.9mol/L, and the mol ratio of magnesium rod and 2-bromothiophene is 4:3, and the mol ratio of compound d and catalyzer is 1:0.03, eluent be normal hexane and methylene dichloride by volume for 9:1 is mixed to get, reaction formula is:
(2) compound f is dissolved in dry DMF, obtains the DMF solution (DMF) that concentration is 0.233mol/L, and be cooled to 0 DEG C, then by phosphorus oxychloride (POCl
3) be slowly added dropwise in DMF solution, the mol ratio of phosphorus oxychloride and compound f is 30:1, dropwises, and is warming up to 50 DEG C of stirring reaction 2h.Be cooled to room temperature, reaction solution is poured in ice-water bath, and add adjust pH extremely neutrality in saturated sodium carbonate solution.After dichloromethane extraction, merge organic phase, after saturated common salt washing, use anhydrous MgSO
4dried overnight.Filter, revolve steaming solvent, be separated through silica gel column chromatography and obtain product g, eluent be sherwood oil and methylene dichloride by volume for 2:1 mix after obtain, reaction formula is:
In an embodiment, for convenience of statement, compd A uses compd A 1 respectively, the expressions such as A2, A3, compd B uses compound B-11 respectively, the expressions such as B2, B3, compound P uses compound P1 respectively, the expressions such as P2, P3, compound b uses compound b1 respectively, the expressions such as b2, b3, compound c uses compound c1 respectively, the expressions such as c2, c3, name is all as the criterion with the title in each embodiment.
Because benzo [1,2-b:4,5-b '] two thiophene-based monomers have good symmetry and planarity, the polymkeric substance therefore based on it has good carrier mobility.And 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants introduce 1,3-bis-mercaptan-2-aldehyde derivative 4,8 of benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone.1,3-bis-mercaptan-2-aldehyde derivative as the good electron donor material of a class, its introducing further enhance benzo [1,2-b:4,5-b '] two thiophene derivants to Electronic Performance.Therefore, the electronics itself had just because of 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and geometrical property, the application that it will expand in polymer solar battery as excellent donor monomer.
By 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and two Thienopyrroles donor monomer as main polymer chain, and using indone class dyestuff as being articulated on side chain by body unit, by main chain and side chain to the interaction of this in acceptor " pushing away-La electronics ", add and reduce the two-dimentional conjugated system that master interchain is formed the energy gap of conjugated polymers simultaneously, substantially increase the light abstraction width of material.
Preparation method of the present invention is simple, and productive rate is high, mild condition, and product is easy to control.
The third aspect, the invention provides a kind of application containing indone-two Thienopyrroles-benzo two thiophene copolymers, described being applied to containing indone-two Thienopyrroles-benzo two thiophene copolymers prepares polymer solar battery active layer material, organic electroluminescence device emitting layer material and organic field effect tube.Described containing indone-two Thienopyrroles-benzo two thiophene copolymers as described in the first aspect of the invention.
One provided by the invention, containing indone-two Thienopyrroles-benzo two thiophene copolymers and preparation method thereof and application, has following beneficial effect:
Of the present invention containing in indone-two Thienopyrroles-benzo two thiophene copolymers contains 4, 8-bis-(1, 3-bis-mercaptan-2-aldehyde) benzo [1, 2-b:4, 5-b '] two thiophene derivants, two Thienopyrroles unit and indone unit, by 4, 8-bis-(1, 3-bis-mercaptan-2-aldehyde) benzo [1, 2-b:4, 5-b '] two thiophene derivants and two Thienopyrroles donor monomer are as main polymer chain, and using propadiene contracting Thiourea dyestuff as being articulated on side chain by body unit, by main chain and side chain to the interaction of this in acceptor " pushing away-La electronics ", add the two-dimentional conjugated system that master interchain is formed, reduce the energy gap of conjugated polymers simultaneously, substantially increase the light abstraction width of material, improve electricity conversion.
Bibliographical information and related application is not had at present openly containing indone-two Thienopyrroles-benzo two thiophene copolymers, it is a kind of new photoelectric material, effciency of energy transfer is high, preparation method is simple, productive rate is high, mild condition, product is easy to control, and makes its having a extensive future in field of photovoltaic materials such as polymer solar battery, organic electroluminescent and organic field effect tubes.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic solar batteries device in embodiment 8;
Fig. 2 is the structural representation of organic electroluminescence device in embodiment 9;
Fig. 3 is the structural representation of organic field effect tube in embodiment 10.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
What the present invention relates to contains indone-two Thienopyrroles-benzo two thiophene copolymers, for having the compound P of following structural formula:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60.
Embodiment 1
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 1(n=10), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-diformazan sulfydryl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A1;
(1) prepare compound 4,8-bis-(4,5-diformazan sulfydryl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c1:
There is provided compound b1 and a, i.e. 2-dimethoxy phosphono-4,5-diformazan sulfydryl-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 1.22g (4.0mmol) b1 is cooled to-78 DEG C; slowly add the cyclohexane solution (4mmol) of 2.7mL1.5MLDA; at-78 DEG C after stirring reaction 3h; the 10mL anhydrous tetrahydrofuran solution adding 0.44g (2.0mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Revolve steaming, remove excessive reaction solution, the crude on silica gel column chromatographic isolation and purification obtained, obtains product c1; Eluent be normal hexane and methylene dichloride by volume for obtaining after 3:1 mixing, productive rate 51%, mass spectrometric measurement result is MS (EI) m/z:577 (M
+); Its reaction formula is as follows:
(2) prepare compd A 1, reaction formula is:
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 1.15g (2.0mmol) c1 is cooled to-78 DEG C; slowly add the hexane solution (4.4mmol) of 1.6mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 2h, then add the Me of 1.2mL (4mmol)
3snCl, returns to room temperature after insulation reaction 0.5h, and continue reaction 24h, obtain product, i.e. A1, mass spectrometric measurement result is MS (EI) m/z:903 (M
+);
Two, prepare compound B-11, structural formula is:
(1) compound g is prepared, i.e. 5-(4-(2,6-dibromo two thieno-[3,2-b:2 ', 3 '-d] pyrroles-4) phenyl) thiophene-2-formaldehyde;
A (), by 0.29g (12.0mmol) magnesium rod, a small amount of iodine powder and 3 2-bromothiophenes are mixed to join in the ether of 10mL drying, under argon shield, and heated and stirred to 40 DEG C backflow.Slowly be added dropwise to the diethyl ether solution (in 10mL ether 1.47g (9.0mmol) 2-bromothiophene) of 2-bromothiophene again, after dropwising, at 40 DEG C, continue back flow reaction 1h, cool for subsequent use.Then the Grignard reagent of this just preparation is slowly added dropwise to containing 2.46g (5.0mmol) 2, the bromo-4-(4-bromophenyl of 6-bis-)-4H-two thieno-[3,2-b:2 ', 3 '-d] pyrroles (d), 0.11g (0.15mmol) Pd (PPh
3)
2cl
2with in the reaction flask of 40mL tetrahydrofuran (THF), stir and back flow reaction 4h at being heated to 60 DEG C, stopped reaction is also cooled to room temperature.Reaction solution is poured into the saturated NH of 50mL
4in the Cl aqueous solution, after extraction into ethyl acetate, merge organic phase and use anhydrous Na
2sO
4dried overnight.Filter, revolve steaming, after removing organic solvent, obtain product f through silica gel column chromatography separating purification, eluent be normal hexane and methylene dichloride by volume for 9:1 mix after obtain, productive rate 25%, MS (EI) m/z:495 (M
+); Its reaction formula is as follows:
B 3.47g (7.0mmol) compound f is dissolved in the DMF of 30mL drying by (), and be cooled to 0 DEG C.Then 20.0mL (210.0mmol) phosphorus oxychloride is slowly added dropwise in reaction mixture, dropwises, be warming up to 50 DEG C of stirring reaction 2h.Be cooled to room temperature, reaction solution is poured in ice-water bath, and add adjust pH extremely neutrality in saturated sodium carbonate solution.After dichloromethane extraction, merge organic phase, after saturated common salt washing, use anhydrous MgSO
4dried overnight.Filter, revolve steaming, except desolventizing, be separated through silica gel column chromatography and obtain product g, eluent be sherwood oil and methylene dichloride by volume for 2:1 mix after obtain, productive rate is 72%, MS (EI) m/z:523 (M
+); Its reaction formula is as follows:
(2) prepare polymer B 1, reaction formula is:
Under nitrogen protection, join in the toluene of 80mL drying by 1.8g (2.0mmol) A1 and 1.05g (2.0mmol) g, bubbling 0.5h removes residual oxygen, then adds rapidly 0.07g (0.1mmol) Pd (PPh
3)
2cl
2form mixed solution, mixed solution bubbling 1h is removed residual oxygen, then back flow reaction 30h at 120 DEG C, after reaction terminates, by mixed solution underpressure distillation, remove excessive toluene, then be added drop-wise in methyl alcohol and carry out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 1 night.Productive rate 52%, product B 1 is carried out gel permeation chromatography (GPC) test, number-average molecular weight ≈ 9380, monodispersity is 1.9.
Three, prepare copolymer p 1, reaction formula is as follows:
There is provided compound h, structural formula is:
164mg (0.175mmol) B1 and 0.68g (3.5mmol) h is joined in 15mL chloroform, then is added dropwise to 0.5mL pyridine, stirring reaction 20h under 40 DEG C of lucifuge conditions.Reaction is revolved steaming, remove portion solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 1 night, productive rate 50%.
Copolymer p 1 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 11150, and polymkeric substance monodispersity is 1.7.
Embodiment 2
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 2(n=60), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-bis-pungent sulfydryl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A2;
(1) prepare compound 4,8-bis-(4,5-bis-pungent sulfydryl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c2:
There is provided compound b2 and a, i.e. 2-dimethoxy phosphono-4,5-bis-pungent sulfydryl-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 2.2g (4.4mmol) b2 is cooled to-78 DEG C; slowly add the cyclohexane solution (6mmol) of 4.0mL1.5MLDA; at-78 DEG C after stirring reaction 3h; the 10mL anhydrous tetrahydrofuran solution adding 0.44g (2.0mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Revolve steaming, remove excessive reaction solution, the crude on silica gel column chromatographic isolation and purification obtained, obtains product c2; Eluent be normal hexane and methylene dichloride by volume for obtaining after 3:1 mixing, productive rate 53%, mass spectrometric measurement result is MS (EI) m/z:970 (M
+); Its reaction formula is as follows:
(2) prepare compd A 2, reaction formula is:
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 1.15g (2.0mmol) c2 is cooled to-78 DEG C; slowly add the hexane solution (4.4mmol) of 1.76mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 2h, then add the Me of 1.3mL (4.4mmol)
3snCl, returns to room temperature after insulation reaction 0.5h, and continue reaction 24h, obtain product A 2, mass spectrometric measurement result is MS (EI) m/z:1295 (M
+);
Two, prepare polymer B 2, structural formula is:
(1) compound g is prepared;
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 2 is prepared; Reaction formula is:
Under nitrogen protection; 2.85g (2.2mmol) A2 and 1.05g (2.0mmol) g is joined in 80mL anhydrous tetrahydro furan; bubbling 0.5h removes residual oxygen, then adds rapidly 46.2mg (0.04mmol) Pd (PPh
3)
4form mixed solution, mixed solution bubbling 1h is removed residual oxygen, back flow reaction 72h at 60 DEG C, after reaction terminates, by mixed solution underpressure distillation, remove excessive tetrahydrofuran (THF), then be added drop-wise in methyl alcohol and carry out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 2 night, productive rate 58%.
Product B 2 is carried out GPC test, number-average molecular weight ≈ 79860, monodispersity is 2.2.
Three, prepare copolymer p 2, reaction formula is as follows:
266mg (0.2mmol) B2 and 873mg (4.5mmol) h is joined in 15mL chloroform, then is added dropwise to 0.56mL pyridine, stirring reaction 22h under 30 DEG C of lucifuge conditions.Reaction is revolved steaming, remove portion solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 2 night, productive rate 52%.
Copolymer p 2 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 90420, and polymkeric substance monodispersity is 1.8.
Embodiment 3
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 3(n=30), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-bis-(16 sulfydryl)-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A3;
(1) prepare compound 4,8-bis-(4,5-bis-(16 sulfydryl)-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c3:
There is provided compound b3 and a, i.e. 2-dimethoxy phosphono-4,5-bis-(16 sulfydryl)-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under argon shield; the 60mL anhydrous tetrahydrofuran solution of 2.18g (3.0mmol) b3 is cooled to-78 DEG C; slowly add the cyclohexane solution (4.5mmol) of 3.0mL1.5MLDA; at-78 DEG C after stirring reaction 2h; the 15mL anhydrous tetrahydrofuran solution adding 0.264g (1.2mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 1h, continue reaction 15h, stopped reaction.Revolve steaming, remove excessive tetrahydrofuran (THF), the crude on silica gel column chromatographic isolation and purification obtained, obtains product c3; Eluent be normal hexane and methylene dichloride by volume for obtaining after 4:1 mixing, productive rate 53%, MS (EI) m/z:1419 (M
+); Its reaction formula is as follows:
(2) prepare compound A-13, reaction formula is:
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 2.84g (2.0mmol) c3 is cooled to-78 DEG C; slowly add the hexane solution (5.0mmol) of 2.0mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 3h, then add the Me of 1.5mL (5.0mmol)
3snCl, returns to room temperature after insulation reaction 1h, and continue reaction 23h, obtain product, i.e. A3, mass spectrometric measurement result is MS (EI) m/z:1744 (M
+);
Two, prepare compd B 3, structural formula is:
(1) compound g is prepared;
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 3 is prepared; Reaction formula is:
Under nitrogen protection; 4.36g (2.5mmol) A3 and 1.05g (2.0mmol) g is joined the dry N of 80mL; in dinethylformamide, bubbling 0.5h removes residual oxygen, then adds rapidly 46.2mg (0.04mmol) Pd (PPh
3)
4form mixed solution, mixed solution bubbling 1h is removed residual oxygen, back flow reaction 24h at 80 DEG C, after reaction terminates, mixed solution underpressure distillation is removed excessive DMF, then be added drop-wise in methyl alcohol and carry out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 3 night, productive rate 48%.
Product B 3 is carried out GPC test, number-average molecular weight ≈ 53400, monodispersity is 1.9.
Three, prepare copolymer p 3, reaction formula is as follows:
356mg (0.2mmol) B3 and 873mg (4.5mmol) h is joined in 15mL chloroform, then is added dropwise to 0.6mL pyridine, stirring reaction 24h under 40 DEG C of lucifuge conditions.Reaction is revolved steaming partial solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 3 night, productive rate 49%.
Copolymer p 3 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 58680, and polymkeric substance monodispersity is 1.72.
Embodiment 4
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 4(n=15), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-dimethyl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A4;
(1) prepare compound 4,8-bis-(4,5-dimethyl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c4:
There is provided compound b4 and a, i.e. 2-dimethoxy phosphono-4,5-dimethyl-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under argon shield; the 50mL anhydrous tetrahydrofuran solution of 1.2g (5.0mmol) b4 is cooled to-78 DEG C; slowly add the cyclohexane solution (6.0mmol) of 2.0mL3MLDA; at-78 DEG C after stirring reaction 3h; the 10mL anhydrous tetrahydrofuran solution adding 0.46g (2.1mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Revolve steaming, remove excessive tetrahydrofuran (THF), the crude on silica gel column chromatographic isolation and purification obtained, obtains product c4; Eluent is obtain after the 4:1 mixing by volume of normal hexane and methylene dichloride, and productive rate 53%, mass spectrometric measurement result is MS (EI) m/z:449 (M
+); Its reaction formula is as follows:
(2) prepare compd A 4, reaction formula is:
Under nitrogen protection; the 40mL anhydrous tetrahydrofuran solution of 0.90g (2.0mmol) c4 is cooled to-78 DEG C; slowly add the hexane solution (5.0mmol) of 2.0mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 2.5h, then add the Me of 1.5mL (5.0mmol)
3snCl, returns to room temperature after insulation reaction 0.7h, and continue reaction 20h, obtain product, i.e. A4, mass spectrometric measurement result is MS (EI) m/z:774 (M
+);
Two, prepare polymer B 4, structural formula is:
(1) compound g is prepared;
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 4 is prepared; Reaction formula is:
Under argon shield, joined by 1.55g (2.0mmol) A4 and 1.05g (2.0mmol) g in the dry DMF of 80mL, bubbling 0.5h removes residual oxygen, then adds catalyst P d rapidly
2(dba)
3(7.3mg, 0.008mmol) and P (o-Tol)
3(48.6mg, 0.16mmol) forms mixed solution, and mixed solution bubbling 1h is removed residual oxygen, and back flow reaction 30h at 80 DEG C, by mixed solution underpressure distillation, removes excessive DMF, then is added drop-wise in methyl alcohol and carries out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 4 night, productive rate 60%.
Product B 4 is carried out GPC test, number-average molecular weight ≈ 12150, monodispersity is 2.0.
Three, prepare copolymer p 4, reaction formula is as follows:
162mg (0.2mmol) B4 and 776mg (4mmol) h is joined in 15mL chloroform, then is added dropwise to 0.6mL pyridine, stirring reaction 24h under 35 DEG C of lucifuge conditions.Reaction is revolved steaming, remove portion solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 4 night, productive rate 47%.
Copolymer p 4 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 14790, and polymkeric substance monodispersity is 1.8.
Embodiment 5
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 5(n=18), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-dihexyl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A5;
(1) prepare compound 4,8-bis-(4,5-dihexyl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c5:
There is provided compound b5 and a, i.e. 2-dimethoxy phosphono-4,5-dihexyl-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under argon shield; the 45mL anhydrous tetrahydrofuran solution of 0.76g (2.0mmol) b5 is cooled to-78 DEG C; slowly add the cyclohexane solution (3.0mmol) of 2.0mL1.5MLDA; at-78 DEG C after stirring reaction 3h; the 6mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Revolve steaming, remove excessive tetrahydrofuran (THF), the crude on silica gel column chromatographic isolation and purification obtained, obtains product c5; Eluent is obtain after the 4:1 mixing by volume of normal hexane and methylene dichloride, productive rate 49%, mass spectrometric measurement result MS (EI) m/z:729 (M
+); Its reaction formula is as follows:
(2) prepare compound A-45, reaction formula is:
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 1.6g (2.2mmol) c5 is cooled to-78 DEG C; slowly add the hexane solution (5.0mmol) of 2.0mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 2h, then add the Me of 1.5mL (5.0mmol)
3snCl, returns to room temperature after insulation reaction 0.5h, and continue reaction 24h, obtain product, i.e. A5, mass spectrometric measurement result is MS (EI) m/z:1055 (M
+);
Two, prepare polymer B 5, structural formula is:
(1) compound g is prepared;
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 5 is prepared; Reaction formula is:
Under nitrogen protection, join in 80mL dry toluene by 2.11g (2.0mmol) A5 and 0.94g (1.8mmol) g, bubbling 0.5h removes residual oxygen, then adds catalyst P d rapidly
2(dba)
3(16.5mg, 0.018mmol) and P (o-Tol)
3(54.8mg, 0.18mmol) forms mixed solution, mixed solution bubbling 1h is removed residual oxygen, back flow reaction 36h at 110 DEG C, after reaction terminates, by mixed solution underpressure distillation, removes excessive toluene, then is added drop-wise in methyl alcohol and carries out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 5 night, productive rate 51%.
Product B 5 is carried out GPC test, number-average molecular weight ≈ 19638, monodispersity is 2.0.
Three, prepare copolymer p 5, reaction formula is as follows:
218mg (0.2mmol) B5 and 873mg (4.5mmol) h is joined in 15mL chloroform, then is added dropwise to 0.6mL pyridine, stirring reaction 22h under 40 DEG C of lucifuge conditions.Reaction is revolved steaming, remove portion solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 5 night, productive rate 52%.
Copolymer p 5 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 22806, and polymkeric substance monodispersity is 1.53.
Embodiment 6
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 6(n=20), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-bis-(hexadecyl)-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A6;
(1) prepare compound 4,8-bis-(4,5-bis-(hexadecyl)-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c6:
There is provided compound b6 and a, i.e. 2-dimethoxy phosphono-4,5-bis-(hexadecyl)-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under argon shield; the 60mL anhydrous tetrahydrofuran solution of 1.32g (2.0mmol) b6 is cooled to-78 DEG C; slowly add the cyclohexane solution (3.0mmol) of 2.0mL1.5MLDA; at-78 DEG C after stirring reaction 2.5h; the 10mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 0.7h, continue reaction 13h, stopped reaction.Revolve steaming, remove excessive tetrahydrofuran (THF), the crude on silica gel column chromatographic isolation and purification obtained, obtains product c6; Eluent be normal hexane and methylene dichloride by volume for obtaining after 4:1 mixing, productive rate 47%, MS (EI) m/z:1290 (M
+); Its reaction formula is as follows:
(2) prepare compd A 6, reaction formula is:
Under nitrogen protection; the 60mL anhydrous tetrahydrofuran solution of 2.58g (2.0mmol) c6 is cooled to-78 DEG C; slowly add the hexane solution (5.0mmol) of 2.0mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 2h, then add the Me of 1.5mL (5.0mmol)
3snCl, returns to room temperature after insulation reaction 0.5h, and continue reaction 24h, obtain product, i.e. A6, mass spectrometric measurement result is MS (EI) m/z:1616 (M
+);
Two, prepare polymer B 6, structural formula is:
(1) compound g is prepared;
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 6 is prepared; Reaction formula is:
Under nitrogen protection, join in 80mL dry toluene by 4.845g (3.0mmol) A6 and 1.05g (2.0mmol) g, bubbling 0.5h removes residual oxygen, then adds catalyst P d rapidly
2(dba)
3(0.1825mg, 2 × 10
-4and P (o-Tol) mmol)
3(0.1215mg, 4 × 10
-4mmol) form mixed solution, mixed solution bubbling 1h is removed residual oxygen, back flow reaction 30h at 110 DEG C, after reaction terminates, by mixed solution underpressure distillation, remove excessive toluene, then be added drop-wise in methyl alcohol and carry out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 6 night, productive rate 45%.
Product B 6 is carried out GPC test, number-average molecular weight ≈ 33040, monodispersity is 2.2.
Three, prepare copolymer p 6, reaction formula is as follows:
330mg (0.2mmol) B6 and 970mg (5mmol) h is joined in 15mL chloroform, then is added dropwise to 0.6mL pyridine, stirring reaction 24h under 40 DEG C of lucifuge conditions.Reaction is revolved steaming, remove portion solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 6 night, productive rate 56%.
Copolymer p 6 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 36560, and polymkeric substance monodispersity is 1.72.
Embodiment 7
A kind of containing indone-two Thienopyrroles-benzo two thiophene copolymers, be designated as copolymer p 7(n=5), structural formula is as follows:
Preparation method comprises the following steps:
One, prepare compound 2,6-bis-(tin trimethyl)-4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as A7;
(1) prepare compound 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, be designated as c7:
There is provided compound b7 and a, i.e. 2-dimethoxy phosphono-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone;
Under argon shield; the 40mL anhydrous tetrahydrofuran solution of 0.42g (2.0mmol) b7 is cooled to-78 DEG C; slowly add the cyclohexane solution (3.0mmol) of 2.0mL1.5MLDA; at-78 DEG C after stirring reaction 3h; the 10mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a again carries out Wittig-Horner reaction; return to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Revolve steaming, remove excessive tetrahydrofuran (THF), the crude on silica gel column chromatographic isolation and purification obtained, obtains product c7; Eluent is obtain after the 5:1 mixing by volume of normal hexane and methylene dichloride, productive rate 55%, mass spectrometric measurement result MS (EI) m/z:393 (M
+); Its reaction formula is as follows:
(2) prepare compd A 7, reaction formula is:
Under nitrogen protection; the 40mL anhydrous tetrahydrofuran solution of 0.79g (2.0mmol) c7 is cooled to-78 DEG C; slowly add the hexane solution (5.0mmol) of 2.0mL2.5Mn-BuLi, at-78 DEG C after stirring reaction 2h, then add the Me of 1.5mL (5.0mmol)
3snCl, returns to room temperature after insulation reaction 0.5h, continues reaction 24h, obtains product, i.e. A7, mass spectrometric measurement result MS (EI) m/z:718 (M
+);
Two, prepare polymer B 7, structural formula is:
(1) compound g is prepared;
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 7 is prepared; Reaction formula is:
Under nitrogen protection, joined by 1.44g (2.0mmol) A7 and 1.05g (2.0mmol) g in the dry DMF of 80mL, bubbling 0.5h removes residual oxygen, then adds catalyst P d rapidly
2(dba)
3(7.3mg, 0.008mmol) and P (o-Tol)
3(48.6mg, 0.16mmol) forms mixed solution, mixed solution bubbling 1h is removed residual oxygen, back flow reaction 30h at 80 DEG C, after reaction terminates, by mixed solution underpressure distillation, removes excessive DMF, then is added drop-wise in methyl alcohol and carries out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Distillation removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product B 7 night, productive rate 59%.
Product B 7 is carried out GPC test, number-average molecular weight ≈ 3775, monodispersity is 2.3.
Three, prepare copolymer p 7, reaction formula is as follows:
151mg (0.2mmol) B7 and 873mg (4.5mmol) h is joined in 15mL chloroform, then is added dropwise to 0.6mL pyridine, stirring reaction 24h under 40 DEG C of lucifuge conditions.Reaction is revolved steaming partial solvent, then is poured into by residual reaction liquid in 50mL methyl alcohol after stopping, and generates and precipitates in a large number, filters, obtains crude product.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product P 7 night, productive rate 71%.
Copolymer p 7 after purifying is carried out GPC test, number-average molecular weight Mn ≈ 4650, and monodispersity is 2.1.
Embodiment 8
That prepares with the embodiment of the present invention 2 contains indone-two Thienopyrroles-benzo two thiophene copolymers P2 for active coating, prepare organic solar batteries device, comprise the substrate of glass 1 stacked gradually, anode 2, middle supplementary layer 3, active coating 4 and negative electrode 5, this device architecture specifically can briefly be described as: substrate of glass/anode/middle supplementary layer/active coating/negative electrode, sees Fig. 1.Wherein, anode 2 is ITO(tin indium oxide), the matrix material that the material employing poly-(3,4-Ethylenedioxy Thiophene) (PEDOT) of middle supplementary layer 3 and polystyrolsulfon acid (PSS) are formed, is called for short PEDOT:PSS; Active coating 4 comprises electron donor material and electron acceptor material, the material of electron donor(ED) be the embodiment of the present invention prepare containing indone-two Thienopyrroles-benzo two thiophene copolymers, the material of electron acceptor(EA) is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM); The material of negative electrode 5 is aluminium.
Wherein, substrate of glass 1, as bottom, chooses ito glass (with anode ITO layer, can buy) during making, after ultrasonic cleaning, with oxygen plasma (oxygen-Plasma) process, to improve its work function; Then the middle supplementary layer 3 of coating on ito glass, is after 1:1 mixing with mass ratio by P2 and PCBM, is spun on PEDOT:PSS rete, obtains active coating 4; Evaporation cathodic metal aluminium 5 under vacuum, obtains organic solar batteries device.
That prepares using embodiment 2 prepares organic solar batteries device containing indone-two Thienopyrroles-benzo two thiophene copolymers P2 as the material of active coating 4, and obtain device, all preparation process are all carried out in the glove box providing nitrogen inert atmosphere.
By the I-E characteristic of Keithley236 current/voltage source-measuring system test component, obtain the performance data of device in table 1.
Table 1 is with the performance data containing the organic solar batteries device that indone-two Thienopyrroles-benzo two thiophene copolymers P2 is prepared for active coating of the present invention
| Multipolymer | Short-circuit current (mA/cm 2) | Open circuit voltage (V) | Packing factor (%) | Energy conversion efficiency (%) |
| P2 | 6.32 | 0.51 | 0.43 | 1.39 |
As seen from the data in Table 1, be 1.39% with the energy conversion efficiency of the organic solar batteries device prepared as active coating containing indone-two Thienopyrroles-benzo two thiophene copolymers P2 of the present invention.Show that indone-two Thienopyrroles-benzene 1,4-Dithiapentalene that contains of the present invention contains 4, 8-bis-(1, 3-bis-mercaptan-2-aldehyde) benzo [1, 2-b:4, 5-b '] two thiophene derivants, two Thienopyrroles unit and indone unit, by 4, 8-bis-(1, 3-bis-mercaptan-2-aldehyde) benzo [1, 2-b:4, 5-b '] two thiophene derivants and two Thienopyrroles donor monomer are as main polymer chain, and using indone unit as being articulated on side chain by body unit, by main chain and side chain to the interaction of this in acceptor " pushing away-La electronics ", add the two-dimentional conjugated system that master interchain is formed, reduce the energy gap of conjugated polymers simultaneously, substantially increase the light abstraction width of material.
Embodiment 9
That prepares with embodiment 4 contains indone-two Thienopyrroles-benzo two thiophene copolymers P4 for luminescent layer, prepare organic electroluminescence device, comprise the glass substrate 01, transparent anode 02, luminescent layer 03, cathode buffer layer 04 and the negative electrode 05 that stack gradually, this device architecture specifically can briefly be described as: substrate of glass/transparent anode/luminescent layer/cathode buffer layer/negative electrode, see Fig. 2, but the structure of practical devices is not limited thereto.Wherein, transparent anode 02 material is tin indium oxide (ITO), luminescent layer 03 material is copolymer p 4 prepared by the embodiment of the present invention 4, spin coating technique is adopted to prepare luminescent layer on ITO, the material of cathode buffer layer 04 is lithium fluoride (LiF), the material of negative electrode 05 is metallic aluminium, and the preparation method of each layer is undertaken by existing preparation method, obtains organic electroluminescence device.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEXCCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency recording organic electroluminescence device is 2.1cd/A, and high-high brightness is 1260cd/m
2.
Embodiment 10
The copolymer p 6 prepared with embodiment 6 is for organic semiconductor layer, prepare organic field effect tube, its structure as shown in Figure 3, comprises the substrate 001, insulation layer 002, decorative layer 003, organic semiconductor layer 004, source electrode (S) 005 and the drain electrode (D) 006 that stack gradually.This device architecture specifically can briefly be described as: substrate/insulation layer/decorative layer/organic semiconductor layer/source/drain electrode, wherein, the material of substrate 001 can be but be not limited to highly doped silicon chip (Si), and the material of insulation layer 002 can be but be not limited to the SiO that thickness is 450nm
2, the material of decorative layer 003 can be but be not limited to octadecyl trichlorosilane alkane (OTS), and the material of organic semiconductor layer 004 is copolymer p 6 prepared by the embodiment of the present invention 6, and source electrode (S) 005 and drain electrode (D) 006 all adopt gold as electrode.
By time of flight method (TimeofFlight, TOF), 7.0 × 10
5vcm
-1electric field in the mean void mobility of organic field effect tube of copolymer p 6 prepared containing the embodiment of the present invention 6 of test be 1.17 × 10
-4m
2/ Vs, shows that indone-two Thienopyrroles-benzo two thiophen polymer that contains prepared by the present invention has good hole transport performance.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1., containing indone-two Thienopyrroles-benzo two thiophene copolymers, it is characterized in that, for having the copolymer p of following structural formula:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60.
2., containing a preparation method for indone-two Thienopyrroles-benzo two thiophene copolymers, it is characterized in that, comprise following operation steps:
(1) polymer B is prepared;
The compd A providing following structural formula to represent respectively and compound g:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched;
In atmosphere of inert gases, be that the compd A of 1:1 ~ 1.5:1 and compound g add in the first organic solvent and dissolve by mol ratio, then add catalyzer and form mixed solution, this mixed solution carries out Stille coupling reaction 24 ~ 72 hours at 60 ~ 120 DEG C, after stopped reaction, separation and purification obtains polymer B, and the structural formula of this polymer B is as follows:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60;
Reaction formula is:
(2) copolymer p is prepared;
The compound h that following structural formula represents is provided:
Be that polymer B and the compound h of 1:20 ~ 1:25 joins in the second organic solvent by mol ratio, after dripping pyridine, at 30 ~ 40 DEG C of stirring reaction 20 ~ 24h, after stopped reaction, separation and purification obtains copolymer p, and reaction formula is:
In formula, R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched, n is the integer between 5 ~ 60.
3. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 2, it is characterized in that, described catalyzer is the mixture of organic palladium or organic palladium and organic phosphine.
4. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 3, it is characterized in that, described organic palladium is two (triphenylphosphine) palladium chloride or tetrakis triphenylphosphine palladium, and the mixture of described organic palladium and organic phosphine is three (dibenzalacetone) two mixture of palladium and three (2-tolyl) phosphine;
In the mixture of described organic palladium and organic phosphine three (dibenzalacetone) two the mol ratio of palladium and three (2-tolyl) phosphine be 1:2 ~ 1:20.
5. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 3, it is characterized in that, the mole dosage of described organic palladium is 0.01% ~ 5% of compound g mole dosage.
6. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 2, it is characterized in that, described first organic solvent is tetrahydrofuran (THF), DMF or toluene; Described second organic solvent is chloroform.
7. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 2, it is characterized in that, step (1) described separation purification method is:
After the completion of reaction, by the underpressure distillation of polymer B reaction solution, remove the first excessive organic solvent, then be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, methanol wash, dry; Then by column chromatography, chloroform drip washing; Distillation removing organic solvent, methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction several, methyl alcohol sedimentation, suction filtration, is pumped through under vacuum pump and obtains product night.
8. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 2, it is characterized in that, step (2) described separation purification method is:
The underpressure distillation of copolymer p reaction solution is removed the second excessive organic solvent, then pours in methyl alcohol, generate and precipitate in a large number, then filter, obtain crude product; After again crude product being dissolved with chloroform, after Teflon filtration membrane filtration, revolve steaming, remove most of chloroform, be more slowly added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, be pumped through under vacuum pump and obtain product night.
9. the preparation method containing indone-two Thienopyrroles-benzo two thiophene copolymers as claimed in claim 2, it is characterized in that, described compd A can be prepared by following methods:
(1) compound a providing following structural formula to represent respectively and compound b:
R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched;
In atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound b is cooled to-78 DEG C, slowly add the cyclohexane solution of lithium diisopropyl amido, at-78 DEG C after stirring reaction 2 ~ 3h, then add the tetrahydrofuran solution of compound a, carry out Wittig-Horner reaction, room temperature is returned to after insulation reaction 0.5 ~ 1h, continue reaction 12 ~ 15h, obtain product, i.e. compound c; Wherein, the mol ratio of lithium diisopropyl amido and b is the mol ratio of 1:1 ~ 1.5:1, a and b is 1:2.0 ~ 1:2.5, and its reaction formula is as follows:
R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched;
(2) in atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound c is cooled to-78 DEG C, slowly add the hexane solution of n-Butyl Lithium, then stirring reaction 2 ~ 3h at-78 DEG C, add trimethyl ammonia chloride tin reagent again, after insulation reaction 0.5 ~ 1h, return to room temperature, continue reaction 20 ~ 24h, obtain product, i.e. compd A; Wherein, the mol ratio of n-Butyl Lithium and c is 2.2:1 ~ 2.5:1, and the mol ratio of trimethyltin chloride and c is 2.0:1 ~ 2.5:1, and its reaction formula is as follows:
R is H, C
1~ C
16the alkyl of straight or branched or C
1~ C
16the alkyl thiol of straight or branched.
10. as claimed in claim 1 containing the application of indone-two Thienopyrroles-benzo two thiophene copolymers in polymer solar battery, organic electroluminescence device and organic field effect tube.
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