CN104769005B - 含噻吩并吡咯二酮单元的苯并二噻吩类共聚物及其制备方法与应用 - Google Patents
含噻吩并吡咯二酮单元的苯并二噻吩类共聚物及其制备方法与应用 Download PDFInfo
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- CN104769005B CN104769005B CN201280076705.0A CN201280076705A CN104769005B CN 104769005 B CN104769005 B CN 104769005B CN 201280076705 A CN201280076705 A CN 201280076705A CN 104769005 B CN104769005 B CN 104769005B
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- Prior art keywords
- alkyl
- thiophene
- methyl
- butyl
- benzo
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229920001577 copolymer Polymers 0.000 title claims abstract description 63
- 229930192474 thiophene Natural products 0.000 title claims abstract description 59
- 125000005605 benzo group Chemical group 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 230000005669 field effect Effects 0.000 claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 99
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 67
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 65
- 125000000217 alkyl group Chemical group 0.000 claims description 64
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 40
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 40
- -1 2,4-dimethyl-3-ethylheptyl Chemical group 0.000 claims description 38
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000000376 reactant Substances 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 20
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 230000004044 response Effects 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 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 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 11
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 125000001544 thienyl group Chemical group 0.000 claims description 10
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 8
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 claims description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 125000005447 octyloxy 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])O* 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- LECHJHHAZKSBIL-UHFFFAOYSA-J N,N-dimethylmethanamine tetrachlorostannane Chemical compound [Sn](Cl)(Cl)(Cl)Cl.CN(C)C LECHJHHAZKSBIL-UHFFFAOYSA-J 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000006837 decompression Effects 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 0 Cc(c(*)c(C(C1=O)=C(c([s]c(*=I)c2*)c2C2=C3SCC(*)=C2*)C3=C1c([s]1)c(*)c(*)c1[Sn](C)(C)C)[s]1)c1[Sn](C)(C)C Chemical compound Cc(c(*)c(C(C1=O)=C(c([s]c(*=I)c2*)c2C2=C3SCC(*)=C2*)C3=C1c([s]1)c(*)c(*)c1[Sn](C)(C)C)[s]1)c1[Sn](C)(C)C 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 7
- 239000012453 solvate Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
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- 241000551547 Dione <red algae> Species 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
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- 230000005611 electricity Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- SLDBAXYJAIRQMX-UHFFFAOYSA-N 3-ethylthiophene Chemical compound CCC=1C=CSC=1 SLDBAXYJAIRQMX-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NSLJAYQJTGJPBW-UHFFFAOYSA-N S1C=CC2=C1C=CS2.C2=CC=CC=C2 Chemical compound S1C=CC2=C1C=CS2.C2=CC=CC=C2 NSLJAYQJTGJPBW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
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- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- ANCBHJKEYPZCTE-UHFFFAOYSA-N ethyl 5-carbamoyl-4-methyl-2-[(2,3,4,5,6-pentafluorobenzoyl)amino]thiophene-3-carboxylate Chemical compound CC1=C(C(N)=O)SC(NC(=O)C=2C(=C(F)C(F)=C(F)C=2F)F)=C1C(=O)OCC ANCBHJKEYPZCTE-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 239000005457 ice water Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 2
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- KWAWUYJHQGFUFM-UHFFFAOYSA-N 2-octan-2-yloxythiophene Chemical compound CC(CCCCCC)OC=1SC=CC=1 KWAWUYJHQGFUFM-UHFFFAOYSA-N 0.000 description 1
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- BYQPEWZIDAQADV-UHFFFAOYSA-N CCCCC(CC(Br)=C1)[S+]1Br Chemical compound CCCCC(CC(Br)=C1)[S+]1Br BYQPEWZIDAQADV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
含噻吩并吡咯二酮单元的苯并二噻吩类共聚物、其制备方法以及该共聚物在聚合物太阳能电池、有机电致发光、有机场效应晶体管、有机光存储、有机非线性材料或有机激光中的应用。
Description
【技术领域】
本发明涉及一种苯并二噻吩类共聚物,尤其涉及一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物及其制备方法与应用。
【背景技术】
有机太阳能电池由于具有无机太阳能电池无法比拟的一些优点,如成本低廉,制作工艺简单,产品重量轻,可大面积柔性制备等优点而作为一种具有潜力的可再生能源受到人们的广泛关注。在过去的十年里,有机太阳能电池的性能提高了,能量转换效率接近10%。
尽管有机太阳能电池的能量转换效率得到了大幅提高,但是,到目前为止,有机太阳能电池的光电转换效率比无机太阳能电池还是要低很多。因此,要想实现有机太阳能电池的商业化,开发新型的有机半导体材料对于提高有机太阳能电池的效率具有重要意义。
由于近年来在共轭聚合物的设计和器件制造工艺上的进步,聚合物太阳能电池的效率已取得很大提高。聚合物太阳能电池未来面临的挑战之一就是合成新型的P-型共轭聚合物,它需要具备以下特点:(a)良好的溶解性,有利于溶剂加工,实现工业化生产;(b)对整个太阳光光谱有宽而强的吸收;(c)高的载流子迁移率,有利于载流子传输。其中如何拓宽聚合物材料的光吸收范围,使其光吸收范围最大程度地覆盖整个太阳光光谱将是研究的重点。在半导体聚合物骨架中选择合适的单体,有利于将聚合物的光吸收范围拓宽到红外、近红外光区。但是,具体如何选择,是现有技术未能解决的问题。
【发明内容】
本发明的一个目的是提供一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物,是苯并二噻吩类单体与噻吩并吡咯二酮类单体系列的共聚物,将其吸收带边沿推向红光及近红外区,以更好的匹配太阳光的发射光谱。
本发明的另一个目的是提供一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备方法。
本发明的又一个目的是提供一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物在聚合物太阳能电池,有机电致发光,有机场效应晶体管,有机光存储,有机非线性材料和有机激光等领域中的应用。
本发明的一个技术方案是,一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物,其具有以下结构:
其中,R1、R2分别选自H或C1至C16的烷基;R3、R4分别选自H、C1至C16的烷基、C1至C16烷氧基或C1至C16烷基取代的噻吩基;R5选自C1至C16的烷基;n为8至82之间的一自然数。
所述的苯并二噻吩类共聚物中,所述烷基为直链烷基、支链烷基或环烷基,所述烷氧基为直链烷氧基或支链烷氧基。
所述的苯并二噻吩类共聚物中,n为9至60之间的一自然数。
所述的苯并二噻吩类共聚物中,R1与R2相同,和/或,R3与R4相同。
所述的苯并二噻吩类共聚物中,R1、R2、R3、R4、R5选自以下一种组合:
R1与R2为H,R3与R4为甲基,R5为正丁基;或者,R1、R2、R3、R4均为H,R5为甲基;或者,R1为乙基,R2为戊基,R3为H,R4为3-甲基噻吩基,R5为2-甲基丁基;或者,R1、R2相同,均为丙基;R3为12烷基;R4为乙氧基;R5为2,4-二甲基-3-乙基庚基;或者,R1为丁基,R2为12烷基,R3为14烷氧基,R4为辛基,R5为2,2,4-三甲基戊基;或者,R1、R2相同,均为H;R3为辛氧基;R4为H;R5为16烷基;或者,R1为己基;R2为H;R3为2-甲基噻吩基;R4为H;R5为辛基;或者,R1为16烷基;R2为H;R3为甲氧基;R4为H;R5为甲基;或者,R1为H;R2为甲基;R3为16烷氧基;R4为H;R5为丁基;或者,R1、R2相同,均为甲基;R3为16烷氧基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3为己基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3为甲基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3、R4相同,均为H;R5为丁基。
本发明的又一个技术方案是,一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备方法,其包括以下步骤,
在无氧的环境下,将以下两种原料:
放入溶剂中,在催化剂的作用下回流反应如下所示:
其中,R1、R2分别选自H或C1至C16的烷基;R3、R4分别选自H、C1至C16的烷基、C1至C16烷氧基或C1至C16烷基取代的噻吩基;R5选自C1至C16的烷基;n为8至82之间的一自然数;其中,M1和M2的摩尔比为1∶1至1.5∶1;所述溶剂选自甲苯、四氢呋喃、苯、N,N-二甲基甲酰胺其中一种或多种;所述催化剂为有机钯催化剂或有机钯催化剂与有机膦配体的混合物,其摩尔添加量为原料M2的0.01%~5%;其中,有机钯催化剂是Pd2(dba)3、Pd(PPh3)4或Pd(PPh3)2Cl2,所述有机钯催化剂与有机膦配体的混合物按摩尔比为1∶2至1∶20;所述有机膦配体包括P(o-Tol)3或三环己基膦;反应温度为60℃至120℃,反应时间为12至72小时。
所述的制备方法中,采用以下步骤合成M1:
S1、将化合物A用适量二氯甲烷溶解后,在氮气保护下,通过注射器逐滴加入到含有1,3-二环己基碳二亚胺和含4-二甲氨基吡啶的无水二氯甲烷中,化合物A:1,3-二环己基碳二亚胺:4-二甲氨基吡啶的摩尔比为3∶3∶1,反应8至24小时,得到化合物B,其反应式如下:
S2、将化合物B和化合物C以摩尔比1∶1加入至溶剂中,所述溶剂为乙醇或丙醇,加热至78~100℃进行回流反应,再加入还原剂,所述还原剂为氢氧化钾或氢氧化钠,其与化合物B的摩尔比为5∶1;当反应液变为墨绿色后再继续反应10分钟,得到化合物D;
S3、在氮气保护下,将化合物D溶解于无水四氢呋喃,溶液冷却至-78℃,缓慢加入含有正丁基锂的正己烷溶液,其中,正丁基锂(n-BuLi)与D的摩尔比为1∶2.5,然后在-78℃下搅拌反应2小时后,再加入三甲基氯化锡试剂,其中,三甲基氯化锡(Me3SnCl)与D的摩尔比为2.5∶1,保温反应0.5小时后恢复到室温,继续反应24小时,得到化合物M1;其反应式如下:
所述的制备方法中,所述烷基为直链烷基、支链烷基或环烷基,所述烷氧基为直链烷氧基或支链烷氧基;并且,n为9至60之间的一自然数。
所述的制备方法中,R1与R2相同,和/或,R3与R4相同;或者,R1、R2、R3、R4、R5选自以下一种组合:R1与R2为H,R3与R4为甲基,R5为正丁基;或者,R1、R2、R3、R4均为H,R5为甲基;或者,R1为乙基,R2为戊基,R3为H,R4为3-甲基噻吩基,R5为2-甲基丁基;或者,R1、R2相同,均为丙基;R3为12烷基;R4为乙氧基;R5为2,4-二甲基-3-乙基庚基;或者,R1为丁基,R2为12烷基,R3为14烷氧基,R4为辛基,R5为2,2,4-三甲基戊基;或者,R1、R2相同,均为H;R3为辛氧基;R4为H;R5为16烷基;或者,R1为己基;R2为H;R3为2-甲基噻吩基;R4为H;R5为辛基;或者,R1为16烷基;R2为H;R3为甲氧基;R4为H;R5为甲基;或者,R1为H;R2为甲基;R3为16烷氧基;R4为H;R5为丁基;或者,R1、R2相同,均为甲基;R3为16烷氧基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3为己基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3为甲基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3、R4相同,均为H;R5为丁基。
本发明的又一个技术方案是,一种采用了任一上述的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物在聚合物太阳能电池、聚合物有机电致发光、聚合物有机场效应晶体管、聚合物有机光存储、聚合物有机非线性材料或聚合物有机激光中的应用。
本发明通过在半导体聚合物骨架中选择合适的单体,有利于将聚合物的光吸收范围拓宽到红外、近红外光区,本发明采用的策略是在聚合物骨架中引入富电子的给体单元和缺电子的受体单元,通过给受体中这种“推-拉电子”的相互作用,降低共轭聚合物的能隙,使其吸收带向红外及近红外低能波段移动。本发明采用苯并二噻吩类衍生物,两个噻吩通过苯环稠环在一个平面内,增强了其平面性和刚性结构,具有较高的光、热和环境稳定性。位于中心的苯环降低了两侧噻吩环的富电子数,使其具有较低的最高已占轨道(HOMO)能级。其具有扩展的共轭大π键体系,π键之间的π-π堆叠具有较高的载流子迁移率,因此,其在有机电子等领域具有广阔的应用价值,能够用于研制开发低成本高效率的有机太阳能电池。
本发明的主要优点还包括以下几项:
1.合成苯并二噻吩类单体M1,噻吩并吡咯二酮类单体M2的路线比较简单且成熟,易通过引入烷基提高产物的溶解性和分子量,以实现可旋涂的聚合物或可旋涂的寡聚物;
2.苯并二噻吩类单体M1是一种优异的给体材料,噻吩并吡咯二酮类单体M2是一种非常优异的受体材料,由单体M1、M2构成的聚合物能够形成一种给体-受体结构,一方面有利于提高了材料的稳定性,另一方面有利于降低材料的能带隙,从而扩大太阳光吸收范围,提高光电转化效率;
3.本发明采取的Stille反应(施蒂勒偶联反应)是一种非常成熟的聚合反应,产率高,且条件温和,易于控制。
【附图说明】
图1是为实施例9制得的有机太阳能电池器件的结构示意图;
图2是为实施例10制得的有机电致发光器件的结构示意图;
图3是为实施例11制得的有机场效应晶体管器件的结构示意图。
【具体实施方式】
下面结合附图,对本发明的具体实施方式进行详细描述。
本发明提供了一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物,首先是通过在苯环上再稠环一个环戊二烯的环内酮结构,增强了稠环体系的平面度和共轭度,从而提高了其载流子迁移率;同时,本申请在环戊二烯酮的两侧引入了噻吩环,并在噻吩上的3,4位引入烷基等修饰来提高其溶解性。然后,本发明还通过苯并噻吩类单体与强的受体单元噻吩并吡咯二酮共聚,形成一种“弱给体-强受体”的共聚物分子,有利于降低分子的光学能隙,扩大材料的光吸收范围,提高材料对太阳光的利用率。
一个例子是,所述的一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物具有以下结构:
上式中,R1、R2相同或不同,R1、R2为H或C1至C16的烷基,包括直链烷基或支链烷基,或者还可以为环烷基等;R3、R4相同或者不同,R3、R4为H或C1至C16的烷基、C1至C16烷氧基、或者C1至C16烷基取代的噻吩基;R5为C1至C16的直链烷基或者支链烷基,或者还可以为C1至C16的环烷基等,例如R5为4-羟基环己基;n为8至82之间的自然数。例如,R1、R2、R3、R4与R5相同,例如R1、R2、R3、R4与R5均为H或者CH3或者乙基等C1至C16的烷基。
又一个例子是,一种制备上述含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备方法,其制备方法如下:
即,将下列两种原料:
放入溶剂中,在催化剂的作用下回流反应,即得含噻吩并吡咯二酮单元的苯并二噻吩类共聚物。其中,M1和M2的摩尔比为1∶1至1.5∶1;例如,M1和M2的摩尔比为1.12∶1、1.2∶1、1.3∶1、1.35∶1、1.4∶1或者1.48∶1等。
例如,M2为1,3-二溴-5-丁基-4H-噻吩[3,4-c]吡咯-4,5-二酮或者1,3-二溴-5-(2-乙基辛烷)-4H-噻吩[3,4-c]吡咯-4,5-二酮等,根据R5而定,其制备方法为现有技术,请参考文献J.Mater.Chem.,2012,22,14639-14644。
优选的,在无氧的环境下,将上述两种原料M1和M2放入溶剂中,在催化剂的作用下回流反应。例如,在氮气环境下或者惰性气体环境下进行上述反应。例如,充氮气。
其中,R1、R2分别选自H或C1至C16的烷基;例如,R1、R2分别选自H或C1至C16的直链烷基或支链烷基,例如氢基、甲基、乙基、丙基、正戊基、2-甲基丁基、异丁基、4-甲基庚基等。括号内表示该苯并二噻吩类共聚物的重复结构单元,*号表示延伸到下一重复结构单元。
R3、R4分别选自H、C1至C16的烷基、C1至C16烷氧基或C1至C16烷基取代的噻吩基;例如,R3、R4分别选自H、C1至C16的直链烷基或支链烷基、C1至C16直链烷氧基或支链烷氧基,或C1至C16的直链烷基或支链烷基取代的噻吩基,例如氢基、正戊基、异丁基、4-甲基庚基、2-甲基4-乙基壬基、异丙氧基、正戊氧基、噻吩基、2-甲基噻吩基、3-乙基噻吩基等。
R5选自C1至C16的烷基;例如,R5选自C1至C16的直链烷基或支链烷基或环烷基,例如甲基、乙基、正戊基、异丁基、4-甲基庚基、2-甲基4-乙基壬基等。
例如,R1、R2、R3、R4与R5相同,例如R1、R2、R3、R4与R5均为H或者CH3或者乙基等C1至C16的烷基。
n为8至82之间的一自然数;例如,n为8、9、10、11、15或55、60、65、72、81、82等,又如,n为9至60之间的一自然数,例如,n为10至50之间的一自然数,例如,n为15至45之间的一自然数,例如,n为18、20、24、25、26、27、29、31、33、35、36、38、42等。通常,根据后续的产品应用,来控制反应物的配比和/或反应时间,从而控制其聚合度。
所述的溶剂为甲苯、四氢呋喃、苯、N,N-二甲基甲酰胺中的一种或多种,反应溶剂足量,足量通常是指完全溶解、完全支持反应等。例如,所述溶剂为甲苯、四氢呋喃、苯、N,N-二甲基甲酰胺,或者,所述溶剂为甲苯与四氢呋喃摩尔比为1∶1至1.5∶1的混合溶剂,又如,所述溶剂为甲苯与四氢呋喃、苯摩尔比为1∶1∶1至2∶1∶2的混合溶剂等,通常来说,优选甲苯、四氢呋喃、苯、N,N-二甲基甲酰胺的摩尔比为1∶1∶1∶1的混合溶剂或者甲苯与苯的摩尔比为1∶1的混合溶剂。通常,该反应必须在无氧的环境下进行;例如,在氮气环境下完成;或者,充入氮气或者惰性气体等。
所述的催化剂为有机钯催化剂或有机钯催化剂与有机膦配体的混合物,其摩尔添加量为原料M2的0.01%~5%。有机钯催化剂是Pd2(dba)3、Pd(PPh3)4或Pd(PPh3)2Cl2;所述的有机钯催化剂与有机膦配体的混合物按摩尔比为1∶2~20。例如,所述催化剂为有机钯催化剂或有机钯催化剂与有机膦配体的混合物,其摩尔添加量为原料M2的0.01%~5%;有机膦配体包括P(o-Tol)3、或三环己基膦)或两者的组合;例如,催化剂的摩尔添加量为原料M2的0.1%、0.12%、0.2%、0.3%、0.45%、0.67%、0.8%、1.1%、2.3%等;其中,有机钯催化剂是Pd2(dba)3、Pd(PPh3)4或Pd(PPh3)2Cl2,所述有机钯催化剂与有机膦配体的混合物按摩尔比为1∶2至1∶20;例如,所述有机钯催化剂与有机膦配体的混合物按摩尔比为1∶2.5、1∶3、1∶5、1∶6.8、1∶8、1∶9、1∶11、1∶14、1∶18或、1∶19.5等。又如,Pd2(dba)3与P(o-Tol)3的摩尔比为1∶3或1∶2。
反应温度为60℃~120℃,反应时间为12~72h。例如,反应温度为61℃、65℃、72℃、78℃、80.5℃、87℃、91℃、105℃或119℃等;又如,反应时间为12.5小时、14小时、22小时、24小时、28小时、37小时、44小时、49小时、56小时、64小时或71小时等。优选的,反应温度与反应时间相匹配,反应温度高则反应时间相对减少,根据充分反应的实际情况进行选择即可。
其中,原料M1的合成步骤如下:
步骤一:将化合物A用适量二氯甲烷溶解后,在氮气保护下,通过注射器逐滴加入到DCC(1,3-二环己基碳二亚胺),DMAP(4-二甲氨基吡啶)的无水二氯甲烷中,摩尔比为A∶DCC∶DMAP=3∶3∶1,反应过夜,得到产物,即化合物B,其反应式如下:
例如,反应时间为8至24小时,例如,化合物A∶DCC∶DMAP的摩尔比为3.5∶3∶1、3∶3∶1.5、或者,2∶2.2∶1等;又如,反应时间为8.5小时、94时、11小时、15.5小时、18小时或22小时等。
步骤二:将化合物B和化合物C以摩尔比1.0∶1.0加入至溶剂中,加热至78~100℃回流,再将适量氢氧化钾/氢氧化钠,其与B的摩尔比为5∶1,当反应液变为墨绿色后再反应8至12min,优选10min,得到产物,即化合物D;其中,溶剂为乙醇、丙醇等,其反应式如下:
例如,化合物B与化合物C的摩尔比为1∶1,加入到乙醇、丙醇或两者的混合物中,例如,乙醇与丙醇摩尔比为1∶1、2.1、1∶2等。加热至78~100℃进行回流反应,例如,均匀加热至80℃、85℃、90℃、91℃、96℃或者99℃进行回流反应;在加热前、加热过程中或者加热达到78℃以上时,加入还原剂;优选的,加热达到78℃以上时再加入还原剂,例如氢氧化钠,其与化合物B的摩尔比为5∶1。
步骤三:在氮气保护下,将化合物D的无水四氢呋喃溶液冷却至-78℃,缓慢加入n-BuLi(正丁基锂)的正己烷溶液,摩尔比为n-BuLi∶D=1∶2.5,加毕,在-78℃下搅拌反应2小时后,再加入三甲基氯化锡试剂,摩尔比为Me3SnCl∶D=2.5∶1,保温反应0.5小时后恢复到室温,继续反应24小时,得到产物,即化合物M1;其反应式如下:
上述各例中,R1与R2相同,并且R3与R4相同;又如,R1与R2相同,R3与R4不相同;或者,R1与R2不相同,R3与R4相同。又如,R1、R2、R3、R4、R5选自以下一种组合:R1与R2为H,R3与R4为甲基,R5为正丁基;或者,R1、R2、R3、R4均为H,R5为甲基;或者,R1为乙基,R2为戊基,R3为H,R4为3-甲基噻吩基,R5为2-甲基丁基;或者,R1、R2相同,均为丙基;R3为12烷基;R4为乙氧基;R5为2,4-二甲基-3-乙基庚基;或者,R1为丁基,R2为12烷基,R3为14烷氧基,R4为辛基,R5为2,2,4-三甲基戊基;或者,R1、R2相同,均为H;R3为辛氧基;R4为H;R5为16烷基;或者,R1为己基;R2为H;R3为2-甲基噻吩基;R4为H;R5为辛基;或者,R1为16烷基;R2为H;R3为甲氧基;R4为H;R5为甲基;或者,R1为H;R2为甲基;R3为16烷氧基;R4为H;R5为丁基;或者,R1、R2相同,均为甲基;R3为16烷氧基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3为己基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3为甲基;R4为H;R5为丁基;或者,R1、R2相同,均为H;R3、R4相同,均为H;R5为丁基。
例如,所述含噻吩并吡咯二酮单元的苯并二噻吩类共聚物具有以下结构:
上式中:R1、R2相同或不同地表示为H或C1至C16的烷基,R3、R4相同或者不同地表示为C1至C16的烷基,C1至C16烷氧基,或者C1至C16烷基取代的噻吩基,R5表示为C1至C16的直链烷基或者支链烷基;n=8-60之间的自然数。
例如,R1、R2分别选自H或C1至C16的烷基;例如,R1、R2分别选自H或C1至C16的直链烷基或支链烷基,例如氢基、甲基、乙基、丙基、正戊基、2-甲基丁基、异丁基、4-甲基庚基、癸基、直链或支链12烷基、直链或支链16烷基等。括号内表示该苯并二噻吩类共聚物的重复结构单元,*号表示延伸到下一重复结构单元。
R3、R4分别选自H、C1至C16的烷基、C1至C16烷氧基或C1至C16烷基取代的噻吩基;例如,R3、R4分别选自H、C1至C16的直链烷基或支链烷基、C1至C16直链烷氧基或支链烷氧基,或C1至C16直链烷基或支链烷基取代的噻吩基,例如氢基、正戊基、异丁基、4-甲基庚基、2-甲基4-乙基壬基、异丙氧基、正戊氧基、噻吩基、2-甲基噻吩基、3-乙基噻吩基等。
R5选自C1至C16的烷基;例如,R5选自C1至C16的直链烷基或支链烷基,例如甲基、乙基、正戊基、异丁基、4-甲基庚基、2-甲基4-乙基壬基等。
例如,上述各例中,所述烷基部分和全部氟化的烷基取代。
同上所述,n为8至82之间的一自然数。通常地,根据后续的产品应用,来控制反应物的配比和/或反应时间,以控制其聚合度。
上述各例中,R1与R2相同,并且R3与R4相同;又如,R1与R2相同,R3与R4不相同;或者,R1与R2不相同,R3与R4相同。
又如,所述的苯并二噻吩类共聚物中,R1与R2为H,R3与R4为甲基,R5为正丁基;或者,R1、R2、R3、R4均为H,R5为甲基。
例如,R1为乙基;R2为戊基;R3为H;R4为3-甲基噻吩基;R5为2-甲基丁基。例如,R2为正戊基或异戊基,即直链烷基或支链烷基均可,下同。
又如,R1、R2相同,均为丙基;R3为12烷基;R4为乙氧基;R5为2,4-二甲基-3-乙基庚基。
又如,R1为丁基,R2为12烷基,R3为14烷氧基,R4为辛基,R5为2,2,4-三甲基戊基。
下面再结合制备方法详细给出几个具体的实施例。
实施例1、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1、R2相同,均为H;R3为辛氧基;R4为H;R5为16烷基,如图所示为2-己基癸基;n=60。
上述含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备步骤如下:
一、1,3-二(2-噻吩)丙酮的制备:
首先,用无水处理过的70mL二氯甲烷将7.6g、36.8mmol的DCC,1.23g、10 mmol的DMAP溶解,在氮气保护下,将溶有5g、35.2 mmol的2-噻吩乙酸的70 mL二氯甲烷溶液逐滴加入至上述反应液中,反应过夜。反应结束后,将反应液过滤,并用正己烷重结晶两次,再经柱层析分离纯化得到产品。
MALDI-TOF-MS(基质辅助激光解吸电离飞行时间质谱,Matrix-Assisted LaserDesorption/Ionization Time of Flight Mass Spectrometry)质荷比(m/z)为222.3(M+).
例如,使用氯化钙或碳酸钾对二氯甲烷进行无水处理,搅拌后放置过夜,然后蒸馏。
二、2,7-二辛氧基苯并[1,2-b:4,3-b’]二噻吩-4,5-二酮的制备:
取25.4g(即60mmol)4,4’-二(2-辛氧基)噻吩加入至干燥的400mL 1,2-二氯乙烷中,即加入至盛有400mL 1,2-二氯乙烷中或加入至盛有400mL经过干燥处理的1,2-二氯乙烷中,下同;再将3mL(即34.5mmol)乙二酰氯在5天内分三次加入至反应瓶中,并在氩气保护下回流反应15天。反应结束后,将反应液冷却至室温,在冰箱里冷冻过夜,过滤得红色固体,依次用正己烷和乙醇洗涤得产物。
MALDI-TOF-MS(m/z)为477.0(M+).
例如,第1天加入1mL乙二酰氯,第3天加入1mL乙二酰氯,第5天加入1mL乙二酰氯;或者,第1天加入1mL乙二酰氯,第2天加入0.5mL乙二酰氯,第5天加入1.5mL乙二酰氯;或者,第1天加入0.5mL乙二酰氯,第3天加入1mL乙二酰氯,第5天加入1.5mL乙二酰氯。
三、2,5-二辛氧基-7,9-二(2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮的制备:
在250mL的单口瓶中依次加入1.2g、5.4 mmol的1,3-二(2-噻吩)丙酮,2.7g、5.4mmol的2,7-二辛氧基-4,5-二酮,40mL乙醇,加热至回流。再将少量氢氧化钾用2mL乙醇溶解,并用注射器逐滴加入至反应瓶中。当反应液变成墨绿色后再反应10min停止反应,并将反应液倒入到冰水浴中。过滤,用乙醇、热的正己烷多次洗涤,干燥得到固体产物。例如,正己烷的温度与反应温度相同,或者正己烷的温度为反应温度±5℃;又如,按摩尔比,氢氧化钾的用量为1,3-二(2-噻吩)丙酮的5倍。
MALDI-TOF-MS(m/z):679.0(M+).
四、2,5-二辛氧基-7,9-二(2-三甲基锡-5-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮的制备:
在氮气保护下,将6.79g、10mmol的2,5-二辛氧基-7,9-二(2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮和120mL无水THF冷却至-78℃,缓慢加入5mL、12mmol的正丁基锂的2.5M正己烷溶液。加毕,在-78℃下保温反应2h后加入4.5mL、15mmol的三甲基氯化锡,保温反应0.5h后自然恢复到室温,继续反应24 h后停止反应。加入50mL正己烷稀释,反应液缓慢倒入到冰水中,萃取得到的有机相分别用5%的NaHCO3,饱和NaCl溶液水洗,无水硫酸镁干燥,过滤,旋蒸,再进行减压蒸馏,蒸出过量的三甲基氯化锡,得到产品。
MALDI-TOF-MS(m/z):1004.6(M+).
五、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.5g、0.5mmol的2,5-二辛氧基-7,9-二(2-三甲基锡-5-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮和0.27g、0.5mmol的1,3-二溴-5-(2-己基癸烷)-4H-噻吩[3,4-c]吡咯-4,5-二酮(如上述反应式的对应结构式所示,下同)加入至盛有10mL干燥甲苯的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂Pd2(dba)3和P(o-Tol)3至反应瓶中;其中,Pd2(dba)323mg,0.025mmol,5%mol;P(o-Tol)3152mg,0.5mmol;Pd2(dba)3与P(o-Tol)3摩尔比为1∶20。
通氮气室温搅拌15min后,加热至80℃回流,搅拌反应72h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd2(dba)3,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
采用凝胶渗透色谱(GPC,Gel Permeation Chromatography)法测量分子量,GPC:Mn=67320,分子量分布系数(PDI)=1.5。
实施例2、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1为己基;R2为H;R3为2-甲基噻吩基;R4为H;R5为辛基,例如1-正辛基;n=55。
上述含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备步骤如下:
一、二(4-二己基-2-噻吩)丙酮的制备:
首先,用无水处理过的70mL二氯甲烷将7.6g DCC,1.23g DMAP溶解,在氮气条件下,将溶有7.6g 4-己基-2-噻吩乙酸的60mL二氯甲烷溶液逐滴加入至上述反应液中,反应过夜。反应结束后,将反应液过滤,并用正己烷重结晶两次,再经柱层析分离纯化得到产品。
MALDI-TOF-MS(m/z):391(M+).
二、2,7-二(2-甲基-5-噻吩)苯并[1,2-b:4,3-b’]二噻吩-4,5-二酮的制备:
取21.5g、60mmol的4,4’-二[2-(2-甲基-5-噻吩)]噻吩加入至350mL干燥的1,2-二氯乙烷中,再将3mL、34.5mmol的乙二酰氯在5天内分三次加入至反应瓶中,并在氩气保护下回流反应15day。反应结束后,将反应液冷却至室温,在冰箱里冷冻过夜,过滤得红色固体,依次用正己烷和乙醇洗涤得产物。
MALDI-TOF-MS(m/z):413.0(M+).
三、2,5-二(2-甲基-5-噻吩)-7,9-二(4-己基-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮的制备:
在250mL的单口瓶中依次加入2.1g、5.4mmol的二(4-己基-2-噻吩)丙酮,2.2g(5.4mmol)2,7-二(2-甲基-5-噻吩)苯并[1,2-b:4,3-b’]二噻吩-4,5-二酮,60 mL乙醇,加热至回流。再将少量氢氧化钾用2 mL乙醇溶解,并用注射器逐滴加入至反应瓶中。当反应液变成墨绿色后再反应10min停止反应,并将反应液倒入到冰水浴中。过滤,用乙醇、热的正己烷多次洗涤,干燥得到固体产物。
MALDI-TOF-MS(m/z):765.0(M+).
四、2,5-二(2-甲基-5-噻吩)-7,9-二(4-己基-2-三甲基锡-5-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮的制备:
在氮气保护下,将7.65g、10mmol的的2,5-二(2-甲基-5-噻吩)-7,9-二(4-己基-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮和150 mL无水THF冷却至-78℃,缓慢加入5mL、12mmol的正丁基锂的正己烷溶液(2.5M)。加毕,在-78℃下保温反应2h后加入4.5mL、15mmol的三甲基氯化锡,保温反应0.5h后自然恢复到室温,继续反应24h后停止反应。加入50mL正己烷稀释,反应液缓慢倒入到冰水中,萃取得到的有机相分别用5%的NaHCO3,饱和NaCl溶液水洗,无水硫酸镁干燥,过滤,旋蒸,再进行减压蒸馏,蒸出过量的三甲基氯化锡,得到产品。
MALDI-TOF-MS(m/z):1093(M+).
五、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.82g、0.75mmol的2,5-二(2-甲基-5-噻吩)-7,9-二(4-己基-2-三甲基锡-5-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.21g、0.5mmol的1,3-二溴-5-辛基-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥四氢呋喃的反应瓶中,即加入至盛有10mL无水四氢呋喃的反应瓶中或加入至盛有10mL干燥处理过的四氢呋喃的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂14mg、0.015mmol、3%mol的Pd2(dba)3和68mg、0.225mmol的P(o-Tol)3至反应瓶中,其中,Pd2(dba)3与P(o-Tol)3摩尔比为1∶15。通氮气室温搅拌15min后,加热至60℃下回流,搅拌反应60h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd2(dba)3,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=56540,PDI=1.8。
实施例3、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1为16烷基;R2为H;R3为甲氧基;R4为H;R5为甲基;n=35。
一、2,5-二甲氧基苯-7,9-二(4-十六烷基-5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮的制备:
合成方法参考前面实施例1中步骤一到步骤四。
MALDI-TOF-MS(m/z):1241(M+).
二、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.74g、0.6mmol的2,5-二甲氧基苯-7,9-二(4-十六烷基-5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.16g、0.5mmol的1,3-二溴-5-甲基-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥DMF的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂Pd2(dba)3和P(o-Tol)3至反应瓶中;其中,Pd2(dba)30.046mg,0.00005mmol,0.01%mol;P(o-Tol)30.0304mg,0.0001mmol;Pd2(dba)3与P(o-Tol)3摩尔比为1∶2。通氮气室温搅拌15min后,加热至120℃回流,搅拌反应48h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd2(dba)3,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=37905,PDI=1.8。
实施例4、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1为H;R2为甲基;R3为16烷氧基;R4为H;R5为2-乙基辛基;n=30。
一、2,5-二(十六烷氧基)-7,9-二(3-甲基-5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮的制备:
合成方法参考前面实施例1中步骤一到步骤四。
MALDI-TOF-MS(m/z):1241(M+).
二、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.62g、0.5mmol的2,5-二(十六烷氧基)-7,9-二(3-甲基-5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.23g、0.5mmol的1,3-二溴-5-(2-乙基辛烷)-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥DMF的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂0.046mg、0.00005mmol、0.01%mol的Pd2(dba)3和0.0304mg、0.0001mmol的P(o-Tol)3至反应瓶中,其中,Pd2(dba)3与P(o-Tol)3摩尔比为1:2。通氮气室温搅拌15min后,加热至120℃回流,搅拌反应48h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd2(dba)3,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=36150,PDI=1.8。
实施例5、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1、R2相同,均为甲基;R3为16烷氧基;R4为H;R5为乙基;n=20。
一、2,5-二(十六烷基)-7,9-二(3,4-二甲基-5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b'1二噻吩-8-酮的制备:
合成方法参考前面实施例1中步骤一到步骤四。
MALDI-TOF-MS(m/z):1237(M+).
二、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.62g、0.5mmol的2,5-二(十六烷基)-7,9-二(3,4-二甲基-5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.17g、0.5mmol的1,3-二溴-5-乙基-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥苯的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂28.9mg,0.025mmol,5%mol的四三苯基磷钯至反应瓶中。通氮气室温搅拌15min后,加热至80℃下回流,搅拌反应24h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂四三苯基磷钯,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=21780,PDI=2.2。
实施例6、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1、R2相同,均为H;R3为己基;R4为H;R5为丁基;n=15。
一、2,5-二己基-7,9-二(5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮的制备:
合成方法参考前面实施例1中步骤一到步骤四。
MALDI-TOF-MS(m/z):900(M+).
二、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.45g、0.5mmol的2,5-二己基-7,9-二(5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.18g、0.5mmol的1,3-二溴-5-丁基-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥甲苯的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂3.5mg,0.005mmol,1%mol的Pd(PPh3)2Cl2至反应瓶中。通氮气室温搅拌15min后,加热至110℃下回流,搅拌反应24h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd(PPh3)2Cl2,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=11700,PDI=2.2。
实施例7、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1、R2相同,均为H;R3为甲基;R4为H;R5为丁基;n=10。
一、2,5-二甲基-7,9-二(5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b’]二噻吩-8-酮的制备:
合成方法参考前面实施例1中的步骤一到步骤四。
MALDI-TOF-MS(m/z):760(M+).
二、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.38g、0.5mmol的2,5-二甲基-7,9-二(5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.18g、0.5mmol的1,3-二溴-5-丁基-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥甲苯的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂11.6mg、0.01mmol、2%mol的四三苯基磷钯至反应瓶中。通氮气室温搅拌15min后,加热至110℃下回流,搅拌反应24h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂四三苯基磷钯,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=12680,PDI=2.2。
实施例8、本实施例公开一种结构如下的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物:
其中,R1、R2相同,均为H;R3、R4相同,均为H;R5为丁基;n=8。
一、7,9-二(5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮的制备:
合成方法参考前面实施例1中步骤一到步骤四。
MALDI-TOF-MS(m/z):732(M+).
二、含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备:
在氮气保护下,将0.37g、0.5mmol的7,9-二(5-三甲基锡-2-噻吩)-8H-环戊二烯苯并[1,2-b:4,3-b']二噻吩-8-酮和0.18g、0.5mmol的1,3-二溴-5-丁基-4H-噻吩[3,4-c]吡咯-4,5-二酮加入至盛有10mL干燥苯的反应瓶中,反应混合物通氮气搅拌15min后,迅速加入催化剂0.29mg、0.00025mmol、0.05%mol的四三苯基磷钯至反应瓶中。通氮气室温搅拌15min后,加热至80℃下回流,搅拌反应12h。反应停止后,待反应液冷却至室温,用减压蒸馏的方法将反应液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌约4h后,逐渐有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂四三苯基磷钯,最后将聚合物溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将聚合物收集烘干。用索氏抽提器将聚合物抽提,从而提高聚合物分子量的单分散性。
GPC:Mn=4896,PDI=2.3。
并且,本发明还提供了上述任一实施例所提供的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物在聚合物太阳能电池、聚合物有机电致发光、聚合物有机场效应晶体管、聚合物有机光存储、聚合物有机非线性材料或聚合物有机激光中的应用。下面给出几个具体的实施例。
实施例9、对以上述实施例1的共聚物,即含噻吩并吡咯二酮单元的苯并二噻吩类共聚物为活性层材料的有机太阳能电池器件,其结构如图1所示。
有机太阳能电池器件的制备:器件结构为玻璃/ITO/PEDOT:PSS/活性层/Al,其中ITO(氧化铟锡)是方块电阻为10-20Ω/口的氧化铟锡,PEDOT为聚(3,4-亚乙二氧基噻吩),PSS为聚(苯乙烯磺酸);ITO玻璃经过超声波清洗后,用氧-Plasma处理,在ITO上涂上PEDOT:PSS,上述实施例1的共聚物作为电子给体材料和PCBM作为电子受体材料采用旋涂技术,金属铝电极通过真空蒸镀技术制备,得到有机太阳能电池器件。
实施例10、对含有上述实施例2的共聚物,即含噻吩并吡咯二酮单元的苯并二噻吩类共聚物为发光层材料的有机电致发光器件,其结构如图2所示。
有机电致发光器件制备:ITO/本发明的共聚物/LiF/Al,在一个玻璃基片上沉积一层方块电阻为10-20Ω/口的氧化铟锡(ITO),作为透明阳极,通过旋涂技术在ITO上制备一层上述实施例2中的共聚物,作为发光层,再在此发光层上真空蒸镀LiF,作为缓冲层,最后蒸镀金属Al,作为器件的阴极。
实施例11、对含有上述实施例3的共聚物,即含噻吩并吡咯二酮单元的苯并二噻吩类共聚物为有机半导体材料的有机场效应晶体管,其结构如图3所示。
有机场效应晶体管的制备:采用高掺杂的硅片(Si)作为衬底,450nm厚的SiO2作为绝缘层,源电极(S),漏电极(D)均采用金作为电极,将上述实施例3的共聚物为有机半导体层旋涂到十八烷基三氯硅烷(OTS)修饰的SiO2上。
申请人相信,本领域的技术人员依据本说明书,足以理解本发明如何实施,并足以判断在权利要求所限定的范围内都可以实施并取得所述的效果,本领域的技术人员能够据此判断和证明上述各例的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物可以用于上述各用途。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制;并且,上面列出的各个技术特征,其相互组合所能够形成各个实施方案,应被视为属于本发明说明书记载的范围。对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物,其特征在于,具有以下结构:
其中,R1、R2分别选自H或C1至C16的烷基;
R3、R4分别选自H、C1至C16的烷基、C1至C16烷氧基或C1至C16烷基取代的噻吩基;
R5选自C1至C16的烷基;
n为8至82之间的一自然数。
2.根据权利要求1所述的苯并二噻吩类共聚物,其特征在于,所述烷基为直链烷基、支链烷基或环烷基,所述烷氧基为直链烷氧基或支链烷氧基。
3.根据权利要求2所述的苯并二噻吩类共聚物,其特征在于,n为9至60之间的一自然数。
4.根据权利要求3所述的苯并二噻吩类共聚物,其特征在于,R1与R2相同,和/或,R3与R4相同。
5.根据权利要求3所述的苯并二噻吩类共聚物,其特征在于,R1、R2、R3、R4、R5选自以下一种组合:
R1与R2为H,R3与R4为甲基,R5为正丁基;或者,
R1、R2、R3、R4均为H,R5为甲基;或者,
R1为乙基,R2为戊基,R3为H,R4为3-甲基噻吩基,R5为2-甲基丁基;或者,
R1、R2相同,均为丙基;R3为C12烷基;R4为乙氧基;R5为2,4-二甲基-3-乙基庚基;或者,
R1为丁基,R2为C12烷基,R3为C14烷氧基,R4为辛基,R5为2,2,4-三甲基戊基;或者,
R1、R2相同,均为H;R3为辛氧基;R4为H;R5为C16烷基;或者,
R1为己基;R2为H;R3为2-甲基噻吩基;R4为H;R5为辛基;或者,
R1为C16烷基;R2为H;R3为甲氧基;R4为H;R5为甲基;或者,
R1为H;R2为甲基;R3为C16烷氧基;R4为H;R5为丁基;或者,
R1、R2相同,均为甲基;R3为C16烷氧基;R4为H;R5为丁基;或者,
R1、R2相同,均为H;R3为己基;R4为H;R5为丁基;或者,
R1、R2相同,均为H;R3为甲基;R4为H;R5为丁基;或者,
R1、R2相同,均为H;R3、R4相同,均为H;R5为丁基。
6.一种含噻吩并吡咯二酮单元的苯并二噻吩类共聚物的制备方法,其特征在于,包括以下步骤,
在无氧的环境下,将以下两种原料:
放入溶剂中,在催化剂的作用下回流反应如下所示:
其中,R1、R2分别选自H或C1至C16的烷基;
R3、R4分别选自H、C1至C16的烷基、C1至C16烷氧基或C1至C16烷基取代的噻吩基;
R5选自C1至C16的烷基;
n为8至82之间的一自然数;
其中,M1和M2的摩尔比为1:1至1.5:1;
所述溶剂选自甲苯、四氢呋喃、苯、N,N-二甲基甲酰胺其中一种或多种;
所述催化剂为有机钯催化剂或有机钯催化剂与有机膦配体的混合物,其摩尔添加量为原料M2的0.01%~5%;
其中,有机钯催化剂是Pd2(dba)3、Pd(PPh3)4或Pd(PPh3)2Cl2,所述有机钯催化剂与有机膦配体的混合物按摩尔比为1:2至1:20;所述有机膦配体包括P(o-Tol)3或三环己基膦;
反应温度为60℃至120℃,反应时间为12至72小时。
7.根据权利要求6所述的制备方法,其特征在于,采用以下步骤合成M1:
S1、将化合物A用适量二氯甲烷溶解后,在氮气保护下,通过注射器逐滴加入到含有1,3-二环己基碳二亚胺和含4-二甲氨基吡啶的无水二氯甲烷中,化合物A:1,3-二环己基碳二亚胺:4-二甲氨基吡啶的摩尔比为3:3:1,反应8至24小时,得到化合物B,其反应式如下:
S2、将化合物B和化合物C以摩尔比1:1加入至溶剂中,所述溶剂为乙醇或丙醇,加热至78~100℃进行回流反应,再加入还原剂,所述还原剂为氢氧化钾或氢氧化钠,其与化合物B的摩尔比为5:1;当反应液变为墨绿色后再继续反应10分钟,得到化合物D;
S3、在氮气保护下,将化合物D溶解于无水四氢呋喃,溶液冷却至-78℃,缓慢加入含有正丁基锂的正己烷溶液,其中,正丁基锂与D的摩尔比为1:2.5,然后在-78℃下搅拌反应2小时后,再加入三甲基氯化锡试剂,其中,三甲基氯化锡与D的摩尔比为2.5:1,保温反应0.5小时后恢复到室温,继续反应24小时,得到化合物M1;其反应式如下:
8.根据权利要求7所述的制备方法,其特征在于,所述烷基为直链烷基、支链烷基或环烷基,所述烷氧基为直链烷氧基或支链烷氧基;并且,n为9至60之间的一自然数。
9.根据权利要求8所述的制备方法,其特征在于,R1与R2相同,和/或,R3与R4相同;或者,R1、R2、R3、R4、R5选自以下一种组合:
R1与R2为H,R3与R4为甲基,R5为正丁基;或者,
R1、R2、R3、R4均为H,R5为甲基;或者,
R1为乙基,R2为戊基,R3为H,R4为3-甲基噻吩基,R5为2-甲基丁基;或者,
R1、R2相同,均为丙基;R3为C12烷基;R4为乙氧基;R5为2,4-二甲基-3-乙基庚基;或者,
R1为丁基,R2为C12烷基,R3为C14烷氧基,R4为辛基,R5为2,2,4-三甲基戊基;或者,
R1、R2相同,均为H;R3为辛氧基;R4为H;R5为C16烷基;或者,
R1为己基;R2为H;R3为2-甲基噻吩基;R4为H;R5为辛基;或者,
R1为C16烷基;R2为H;R3为甲氧基;R4为H;R5为甲基;或者,
R1为H;R2为甲基;R3为C16烷氧基;R4为H;R5为丁基;或者,
R1、R2相同,均为甲基;R3为C16烷氧基;R4为H;R5为丁基;或者,
R1、R2相同,均为H;R3为己基;R4为H;R5为丁基;或者,
R1、R2相同,均为H;R3为甲基;R4为H;R5为丁基;或者,
R1、R2相同,均为H;R3、R4相同,均为H;R5为丁基。
10.权利要求1至5任一所述的含噻吩并吡咯二酮单元的苯并二噻吩类共聚物在聚合物太阳能电池、聚合物有机电致发光、聚合物有机场效应晶体管、聚合物有机光存储、聚合物有机非线性材料或聚合物有机激光中的应用。
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US9328203B2 (en) * | 2012-11-30 | 2016-05-03 | Ocean's King Lighting Science & Technology Co., Ltd. | Benzodithiophene based copolymer containing pyridino [2,1,3] thiadiazole units and preparing method and applications thereof |
CN105098596B (zh) * | 2015-09-14 | 2019-04-16 | 深圳硅基传感科技有限公司 | 一种降低氧化铟锡/金属电极对有机激光增益层产生的光损耗的方法 |
CN105957964A (zh) * | 2016-05-03 | 2016-09-21 | 南京邮电大学 | 一种柔性有机半导体激光器及其制作方法 |
JP2018174279A (ja) * | 2017-03-31 | 2018-11-08 | 国立大学法人九州大学 | 有機半導体レーザー素子 |
CN114507336B (zh) * | 2022-01-18 | 2023-08-22 | 常州大学 | 一种含氟近红外吸收共轭聚合物及其制备方法 |
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KR101128943B1 (ko) * | 2007-04-13 | 2012-03-27 | 주식회사 엘지화학 | 디옥시피롤기를 포함하는 헤테로고리 화합물 및 이를이용한 유기 전자 소자 |
US8927971B2 (en) * | 2009-04-06 | 2015-01-06 | University Of Kentucky Research Foundation | Semiconducting compounds and devices incorporating same |
WO2011028827A2 (en) * | 2009-09-04 | 2011-03-10 | Plextronics, Inc. | Organic electronic devices and polymers, including photovoltaic cells and diketone-based polymers |
JP2011168747A (ja) * | 2010-02-22 | 2011-09-01 | Kyoto Univ | 共役系高分子、該共役系高分子を用いた有機薄膜太陽電池 |
US8729220B2 (en) | 2010-03-31 | 2014-05-20 | Basf Se | Annellated dithiophene copolymers |
CN102344550B (zh) | 2010-07-30 | 2013-03-27 | 海洋王照明科技股份有限公司 | 含噻吩并吡咯二酮单元苝四羧酸二酰亚胺共聚物及其制备方法和应用 |
EP2706077A4 (en) * | 2011-03-11 | 2014-09-17 | Kuraray Co | PI ELECTRON CONJUGATED BLOCK COPOLYMER AND PHOTOELECTRIC CONVERSION ELEMENT |
JP2012207104A (ja) * | 2011-03-29 | 2012-10-25 | Mitsubishi Chemicals Corp | ヨウ素化縮合チオフェン化合物を用いたコポリマーの製造方法、及びヨウ素化ジオキソピロロチオフェン化合物 |
KR20140043387A (ko) * | 2011-05-16 | 2014-04-09 | 메르크 파텐트 게엠베하 | 공액 중합체 |
US9328203B2 (en) * | 2012-11-30 | 2016-05-03 | Ocean's King Lighting Science & Technology Co., Ltd. | Benzodithiophene based copolymer containing pyridino [2,1,3] thiadiazole units and preparing method and applications thereof |
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CN104769005A (zh) | 2015-07-08 |
EP2927259A1 (en) | 2015-10-07 |
EP2927259A4 (en) | 2016-08-24 |
JP6096314B2 (ja) | 2017-03-15 |
WO2014082310A1 (zh) | 2014-06-05 |
US20150307663A1 (en) | 2015-10-29 |
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