WO2014082309A1 - 含吡啶并[2,1,3]噻二唑单元的苯并二噻吩类共聚物及其制备方法与应用 - Google Patents
含吡啶并[2,1,3]噻二唑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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- WO2014082309A1 WO2014082309A1 PCT/CN2012/085681 CN2012085681W WO2014082309A1 WO 2014082309 A1 WO2014082309 A1 WO 2014082309A1 CN 2012085681 W CN2012085681 W CN 2012085681W WO 2014082309 A1 WO2014082309 A1 WO 2014082309A1
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- Prior art keywords
- reaction
- same
- alkyl
- alkoxy
- organic
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 56
- FLJNBJNOOHZYSZ-UHFFFAOYSA-N [1,2,5]thiadiazolo[3,4-b]pyridine Chemical group C1=CC=NC2=NSN=C21 FLJNBJNOOHZYSZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 10
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 title abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 82
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 45
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 15
- 230000005669 field effect Effects 0.000 claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 109
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 23
- 229910052763 palladium Inorganic materials 0.000 claims description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 238000003756 stirring Methods 0.000 claims description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 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 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000002994 raw material Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 229910000073 phosphorus hydride Inorganic materials 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
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000005401 electroluminescence Methods 0.000 claims description 3
- NGWRWXZTTCRVJE-UHFFFAOYSA-N 1,2,3,6-tetrahydrophosphinine Chemical compound C1CC=CCP1 NGWRWXZTTCRVJE-UHFFFAOYSA-N 0.000 claims 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims 1
- 229940049706 benzodiazepine Drugs 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 38
- 239000007787 solid Substances 0.000 description 25
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 22
- -1 4-methylheptyl Chemical group 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- BFJMHTOBRRZELQ-UHFFFAOYSA-N 3-iodo-2h-pyrazolo[3,4-c]pyridine Chemical compound N1=CC=C2C(I)=NNC2=C1 BFJMHTOBRRZELQ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 125000003396 thiol group Chemical class [H]S* 0.000 description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
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- 229920000547 conjugated polymer Polymers 0.000 description 3
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- 239000011521 glass Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 0 *c1c[s]c(C(C(C(c2c(*)c(I)c[s]2)=C23)=O)=C2c([s]c(*)c2*)c2-c2c3[s]c(*)c2*)c1* Chemical compound *c1c[s]c(C(C(C(c2c(*)c(I)c[s]2)=C23)=O)=C2c([s]c(*)c2*)c2-c2c3[s]c(*)c2*)c1* 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HPARLNRMYDSBNO-UHFFFAOYSA-N 1,4-benzodioxine Chemical compound C1=CC=C2OC=COC2=C1 HPARLNRMYDSBNO-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
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- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
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- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SVUOLADPCWQTTE-UHFFFAOYSA-N 1h-1,2-benzodiazepine Chemical compound N1N=CC=CC2=CC=CC=C12 SVUOLADPCWQTTE-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- YBURIHOCWHBUIE-UHFFFAOYSA-N 2-(4-hexylthiophen-2-yl)acetic acid Chemical compound CCCCCCC1=CSC(CC(O)=O)=C1 YBURIHOCWHBUIE-UHFFFAOYSA-N 0.000 description 1
- SMJRBWINMFUUDS-UHFFFAOYSA-N 2-thienylacetic acid Chemical compound OC(=O)CC1=CC=CS1 SMJRBWINMFUUDS-UHFFFAOYSA-N 0.000 description 1
- GZLSEZBHSMOPKI-UHFFFAOYSA-N 3-pyridin-2-yl-1,2,5-thiadiazole Chemical group C1=NSN=C1C1=CC=CC=N1 GZLSEZBHSMOPKI-UHFFFAOYSA-N 0.000 description 1
- LEHZIBSAFRVAJP-UHFFFAOYSA-N Brc(c1n[s]nc11)cnc1Br Chemical compound Brc(c1n[s]nc11)cnc1Br LEHZIBSAFRVAJP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZDQLBBUJZAHKIG-UHFFFAOYSA-N C=[Br]c(c1n[s]nc11)ncc1Br Chemical compound C=[Br]c(c1n[s]nc11)ncc1Br ZDQLBBUJZAHKIG-UHFFFAOYSA-N 0.000 description 1
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- YVQBDVYOWONXBJ-UHFFFAOYSA-N C[Sn](C)(C)c1ccc(C(C2=C)=C(c([s]cc3)c3C3=C4SCC=C3)C4=C2c([s]2)ccc2[Sn](C)(C)C)[s]1 Chemical compound C[Sn](C)(C)c1ccc(C(C2=C)=C(c([s]cc3)c3C3=C4SCC=C3)C4=C2c([s]2)ccc2[Sn](C)(C)C)[s]1 YVQBDVYOWONXBJ-UHFFFAOYSA-N 0.000 description 1
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- CHXARDKIHSVFDK-UHFFFAOYSA-N hexylphosphane Chemical compound CCCCCCP CHXARDKIHSVFDK-UHFFFAOYSA-N 0.000 description 1
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- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- UDJFFSGCRRMVFH-UHFFFAOYSA-N pyrido[2,3-d]pyrimidine Chemical compound N1=CN=CC2=CC=CN=C21 UDJFFSGCRRMVFH-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- NYERMPLPURRVGM-UHFFFAOYSA-N thiazepine Chemical compound S1C=CC=CC=N1 NYERMPLPURRVGM-UHFFFAOYSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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Definitions
- the present invention relates to a benzodithiophene copolymer, and more particularly to a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit, and a preparation method and application thereof.
- Organic solar cells have attracted a lot of attention as potential renewable energy sources due to their incomparable advantages such as low cost, simple manufacturing process, light weight, and large-area flexible preparation. In the past decade, the performance of organic solar cells has improved and the energy conversion efficiency is close to 10%.
- An object of the present invention is to provide a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit which is a benzodithiophene monomer and a pyrido[2, 1,3]
- the copolymer of the thiadiazole monomer series pushes the absorption band edge toward the red and near-infrared regions to better match the emission spectrum of sunlight.
- Another object of the present invention is to provide a process for producing a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit.
- Still another object of the present invention is to provide a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit at Polymer solar cells, organic electroluminescence, organic field effect transistors, organic optical storage, organic nonlinear materials and organic laser applications.
- One embodiment of the present invention is a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit having the following structure:
- R 2 are respectively selected from H or [! The alkyl group to ⁇ ; R 3 and R 4 are respectively selected from 11, ⁇ ! An alkyl group, a Ci to C 16 alkoxy group or a d to C 16 alkyl group-substituted thiol group; X is N and Y is CH, or X is CH and Y is N; n is between 7 and 80 A natural number.
- the alkyl group is a linear alkyl group or a branched alkyl group
- the alkoxy group is a linear alkoxy group or a branched alkoxy group
- n is a natural number between 8 and 60.
- R 2 In the benzodithiophene-based copolymer, it is the same as R 2 and/or R 3 is the same as R 4 .
- R 2 , R 3 and R 4 are selected from the group consisting of: 11 and R 3 and R 4 are methyl groups; or, Ri, R 2 , R 3 and R 4 are both Is H; or, is ethyl, R 2 is pentyl, R 3 is H, R 4 is 3-methyl p-sail; or, R 2 is the same, all are propyl; R 3 is 12 alkyl; R4 is ethoxy; or, is butyl, R 2 is 12 alkyl, R 3 is 14 alkoxy, R 4 is octyl; or, R 2 is the same, all are H; R 3 is octyloxy; R4 is H; or a hexyl group; R 2 is H; R 3 is 2-methyl-thiazol Yu group; R4 is H; or 16 alkyl group; R 2 is H; R 3 is methoxy; R4 is H; or, R 2 is a
- a method for preparing a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit which comprises the following steps,
- R 2 are respectively selected from H or [! The alkyl group to ⁇ ; R 3 and R 4 are respectively selected from 11, ⁇ ! An alkyl group, a Ci to C 16 alkoxy group or a d to C 16 alkyl group-substituted thiol group; X is N and Y is CH, or X is CH and Y is N; n is between 7 and 80 a natural number; wherein, the molar ratio of M1 to M2 is 1:1 to 1.5:1; the solvent is selected from one or more of toluene, tetrahydrofuran, benzene, N,N-dimethylformamide;
- the catalyst is an organic palladium catalyst or a mixture of an organic palladium catalyst and an organophosphine ligand, and the molar addition amount is 0.01% to 5% of the raw material M2; wherein, the organic palladium catalyst is Pd 2 (dba) 3 , Pd (PPh 3 ) 4 Or Pd(
- 1,3-dicyclohexylcarbodiimide 4-dimethylaminopyridine in a molar ratio of 3:3:1
- the reaction is carried out for 8 to 24 hours to obtain a compound B, which has a reaction formula: S2
- the compound B and the compound C are added to the solvent in a molar ratio of 1:1, the solvent is ethanol or propanol, heated to 78 ⁇ 100 ° C for reflux reaction, and then a reducing agent is added, the reducing agent is hydrogen Potassium oxide or sodium hydroxide, its ratio to compound B is 5:1; when the reaction liquid turns into dark green, the reaction is continued for another 10 minutes to obtain compound D;
- the alkyl group is a linear alkyl group or a branched alkyl group
- the alkoxy group is a linear alkoxy group or a branched alkoxy group
- n is between 8 and 60 A natural number.
- R 3 and R 4 are the same; or, R 2 , R 3 , and R4 are selected from the following combination: and R 3 and R 4 are methyl; or, Ri , R 2 , R 3 , R4 are all H; or, is ethyl, R 2 is pentyl, R 3 is H, R 4 is 3-methylthiamethyl; or, R 2 is the same, both are propyl R 3 is 12 alkyl; R 4 is ethoxy; or, is butyl, R 2 is 12 alkyl, R 3 is 14 alkoxy, R 4 is octyl; or, R 2 is the same, both are H ; R 3 is octyl group; R4 is H; or a hexyl group; R 2 is H; R is 2-methylthiazol-Yu.
- R4 is H; or 16 alkyl group; R 2 is H; R 3 is methoxy; R4 is H; or, is H; R 2 is methyl; R 3 is 16 alkoxy; R 4 is H; or, R 2 is the same, all are methyl; R 3 is 16 alkoxy; R 4 is H; or, R 2 is the same, Is R; R 3 is hexyl; R 4 is H; or R 2 is the same, all are H; R 3 is methyl; R 4 is H; or, R 2 is the same, all are H; R 3 and R 4 are the same , all are H.
- a benzodithiophene copolymer containing any of the above pyridyl[2,1,3]thiadiazole units is used in a polymer solar cell or a polymer organic battery.
- the present invention facilitates broadening the light absorption range of the polymer to the infrared and near-infrared light regions by selecting a suitable monomer in the semiconductor polymer backbone.
- the strategy of the present invention is to introduce an electron-rich into the polymer backbone.
- the bulk unit and the electron-deficient acceptor unit reduce the energy gap of the conjugated polymer by the interaction of the "push-pull electron" in the acceptor, causing the absorption band to move toward the infrared and near-infrared low energy bands.
- the present invention employs a benzodithiophene derivative in which two thiophenes are fused through a benzene ring in a plane to enhance their planarity and rigidity, and have high light, heat and environmental stability.
- the centrally located benzene ring reduces the number of electrons rich in the thiophene ring on both sides, giving it a lower maximum occupied orbital (HOMO) level.
- HOMO maximum occupied orbital
- benzodiazepin plug Yu monomer Ml p is an excellent donor material
- pyrido [2,1,3] thiadiazole-based monomer M2 receptor is a very good material from the monomers
- the polymer composed of Ml and M2 can form a donor-acceptor structure, which is beneficial to improve the stability of the material, and on the other hand, it can reduce the band gap of the material, thereby expanding the solar absorption range and improving the photoelectricity. Conversion efficiency;
- the Stille reaction (Stiler coupling reaction) extracted by the present invention is a very mature polymerization reaction with high yield, mild conditions and easy control.
- Example 1 is a schematic structural view of an organic solar cell device obtained in Example 9;
- Example 10 is a schematic structural view of an organic electroluminescent device prepared in Example 10; 3 is a schematic view showing the structure of an organic field effect transistor device produced in the eleventh embodiment.
- the present invention provides a benzodithiophene-based copolymer containing a pyrido[2,1,3]thiadiazole unit, first by re-condensing a cyclopentadiene cyclic ketone structure on a benzene ring.
- the flatness and conjugate degree of the fused ring system are enhanced, thereby increasing the carrier mobility thereof.
- the present application introduces a thiophene ring on both sides of the cyclopentadienone, and 3, 4 on the thiophene.
- a modification such as an alkyl group is introduced to increase the solubility.
- the present invention also forms a "weak donor-strong acceptor" copolymer molecule by copolymerizing a benzothiophene monomer with a strong acceptor unit pyrido[2,1,3]thiadiazole. It is beneficial to reduce the optical energy gap of the molecule, expand the light absorption range of the material, and improve the utilization of sunlight by the material.
- the benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit has the following structure:
- R 2 is the same or different, and R 2 is H or an alkyl group of [ 16 , including a linear alkyl group or a branched alkyl group, or may also be a cycloalkyl group; R 3 and R 4 are the same or Different, R 3 , R4 are H or C! to C 16 alkyl, d to C 16 alkoxy, or d to C 16 alkyl substituted silyl; X is N and Y is CH, or X is CH and Y are N; n is a natural number between 8 and 60.
- Still another example is a method for preparing a benzodithiophene copolymer containing the above pyridyl[2,l,3] p -soxadiazole unit, which is prepared as follows:
- the mixture is placed in a solvent and refluxed under the action of a catalyst to obtain a benzodithiboxene copolymer containing a pyrido[2,1,3]thiadiazole unit.
- the molar ratio of M1 to M2 is 1:1 to 1.5:1; for example, the molar ratio of M1 to M2 is 1.12:1, 1.2:1, 1.3:1, 1.35:1, 1.4:1 or 1.48:1, etc. .
- M2 is 4,7-dibromo-[1,2,5]thiadiazole [3,4-c]pyridine, and its preparation method is a prior art.
- bismuth replaces bromine with chlorine.
- the above two raw materials M1 and M2 are placed in a solvent in an oxygen-free environment, and the reaction is refluxed under the action of a catalyst.
- the above reaction is carried out under a nitrogen atmosphere or an inert gas atmosphere.
- nitrogen is charged.
- R 2 is each independently selected from H or to an alkyl group; for example, R 2 is independently selected from H or to a linear alkyl or branched alkyl group of 16 , such as a hydrogen group, a methyl group, an ethyl group, or a C group.
- Base n-pentyl, 2-methylbutyl, isobutyl, 4-methylheptyl and the like.
- the repeating structural unit of the benzodithiophene-based copolymer is indicated in parentheses, and the * sign indicates extension to the next repeating structural unit.
- R 3 and R 4 are each independently selected from the group consisting of an alkyl group of 11 to a C 16 alkoxy group or a C 16 alkyl group substituted with a C 16 alkyl group; for example, R 3 and R 4 are each independently selected from a straight chain of H to C 16 .
- n is a natural number between 7 and 80; for example, n is a natural number between 8 and 60, for example, n is between 10 and 50 A natural number, for example, n is a natural number between 15 and 45, for example, n is 18, 20, 24, 25, 26, 27, 29, 31, 33, 35, 36, 38, 42 and the like.
- the ratio of reactants and/or reaction time is controlled based on subsequent product applications to control the degree of polymerization.
- the solvent is one or more of toluene, tetrahydrofuran, benzene, N,N-dimethylformamide, and the reaction solvent is sufficient.
- the sufficient amount generally means complete dissolution, complete support reaction, and the like.
- the solvent is toluene, tetrahydrofuran, benzene, N,N-dimethylformamide, or the solvent is a mixed solvent of a molar ratio of toluene to tetrahydrofuran of 1:1 to 1.5:1, and, for example, the solvent is a molar ratio of toluene to tetrahydrofuran and benzene: a mixed solvent of 1:1 to 2:1:2, etc., generally, a mixed solvent of toluene, tetrahydrofuran, benzene, N,N-dimethylformamide in a molar ratio of 1:1:1:1 or toluene is preferred.
- the catalyst is an organic palladium catalyst or a mixture of an organic palladium catalyst and an organophosphine ligand, and the molar addition amount is 0.01% to 5% of the raw material M2.
- the organic palladium catalyst is Pd 2 (dba) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 ; the molar ratio of the mixture of the organic palladium catalyst and the organophosphine ligand is 1:2-20.
- the catalyst is an organic palladium catalyst or a mixture of an organic palladium catalyst and an organophosphine ligand in a molar addition amount of 0.01% to 5% of the raw material M2; and the organic phosphine ligand includes P(o-Tol) 3 or a tricyclic ring. Hexylphosphine) or a combination of the two; for example, the molar addition amount of the catalyst is 0.1%, 0.12%, 0.2%, 0.3%, 0.45%, 0.67%, 0.8%, 1.1%, 2.3%, etc.
- the organic palladium catalyst is Pd 2 (dba) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2
- the molar ratio of the mixture of the organic palladium catalyst and the organophosphine ligand is 1:2 to 1:20.
- the molar ratio of the mixture of the organic palladium catalyst and the organophosphine ligand is 1:2.5, 1:3, 1:5, 1:6.8, 1:8, 1:9, 1:11, 1:14 , 1:18 or 1:19.5.
- the molar ratio of Pd 2 (dba) 3 to P(o-Tol) 3 is 1:3 or 1:2.
- the reaction temperature is 60 ° C ⁇ 120 ° C, and the reaction time is 12 to 72 h.
- the reaction temperature is 61 ° C, 65 V, 72 ° C, 78 ° C, 80.5 ° C, 87 ° C, 91 ° C, 105 ° C or 119 ° C, etc.; for example, the reaction time is 12.5 hours, 14 hours, 22 hours, 24 hours, 28 hours, 37 hours, 44 hours, 49 hours, 56 hours, 64 hours or 71 hours, etc.
- the reaction temperature is matched with the reaction time, and when the reaction temperature is high, the reaction time is relatively decreased, and the selection can be carried out according to the actual conditions of the sufficient reaction.
- the synthesis steps of the raw material M1 are as follows:
- Step 1 After dissolving Compound A in an appropriate amount of dichloromethane, it was added dropwise to a DCC (1,3-dicyclohexylcarbodiimide), DMAP (4-dimethylaminopyridine) by a syringe under a nitrogen atmosphere.
- DCC 1,3-dicyclohexylcarbodiimide
- DMAP 4-dimethylaminopyridine
- the reaction time is 8 to 24 hours, for example, the molar ratio of the compound A: DCC: DMAP is 3.5: 3: 1, 3: 3: 1.5, or 2: 2.2: 1; for example, the reaction time is 8.5. Hours, 9 hours, 11 hours, 15.5 hours, 18 hours or 22 hours, etc.
- Step 2 Add Compound B and Compound C to the solvent at a molar ratio of 1.0:1.0, heat to 78 ⁇ 100 ° C, reflux, and then add appropriate amount of potassium hydroxide / sodium hydroxide, the molar ratio of B to B: 5:1 When the reaction liquid turns into dark green and then reacts for 8 to 12 minutes, preferably 10 minutes, to obtain a product, that is, compound D; wherein, the solvent is ethanol, propanol, etc.,
- the molar ratio of the compound B to the compound C is 1:1, added to ethanol, propanol or a mixture of the two, for example, the molar ratio of ethanol to propanol is 1:1, 2:1, 1:2, etc. .
- Heating to 78 ⁇ 100 ° C for reflux reaction for example, heating to 80 ° C, 85 ° C, 90 ° C, 91 ° C, 96 ° C or 99 ° C for reflux reaction; before heating, during heating Or, when the heating reaches 78 ° C or higher, a reducing agent is added; preferably, a reducing agent such as sodium hydroxide is added when the heating reaches 78 ° C or higher, and the molar ratio thereof to the compound B is 5:1.
- R 3 and R4 are the same; and, like, R 3 and R 4 are different; or, unlike R 4 , R 3 is the same as R 4 .
- R 2 , R 3 , and R 4 are selected from the group consisting of: Ri and R 2 are H, and R 3 and R 4 are methyl; or Ri, R 2 , R 3 , and R 4 are both H; Is ethyl, R 2 is pentyl, R 3 is H, R 4 is 3-methylthienyl; or, R 2 is the same, all are propyl; R 3 is 12 alkyl; R 4 is ethoxy; or, butyl, R 2 is 12 alkyl, R 3 is C14 alkyl, R4 is octyl; or, the same as R 2, are both H; R 3 is octyl group; R4 is H; or a hexyl group; R 2 is H; R 3 2-methyl-thiazol Yu group; R
- the pyridinium containing [2, 1, has the following structure:
- R 2 is the same or differently represented as H or to an alkyl group
- R 3 and R 4 are the same or differently represented as an alkyl group of d to C 16 , a Ci to C 16 alkoxy group, or a d to C a 16 alkyl-substituted thiol group
- X is N and Y is CH, or X is CH and Y is N
- n a natural number between 8 and 60.
- R 2 is each selected from H or C! to C 16 alkyl; for example, R 2 is independently selected from H or C! to C 16 linear alkyl or branched alkyl, such as hydrogen, A Base, ethyl, propyl, n-pentyl, 2-methylbutyl, isobutyl, 4-methylheptyl, decyl, linear or branched 12 alkyl, straight or branched 16 alkyl Wait.
- the repeating structural unit of the benzodithiophene-based copolymer is indicated in parentheses, and the * sign indicates extension to the next repeating structural unit.
- R 3 and R 4 are each independently selected from the group consisting of an alkyl group of 11 to a C 16 alkoxy group or a C 16 alkyl group substituted with a C 16 alkyl group; for example, R 3 and R 4 are each independently selected from a straight chain of H to C 16 .
- An alkyl or branched alkyl group, a C 16 linear alkoxy group or a branched alkoxy group, or a C 16 linear alkyl group or a branched alkyl group substituted with a thiol group for example, a hydrogen group, an n-pentyl group, Isobutyl, 4-methylheptyl, 2-methyl 4-ethylindenyl, isopropoxy, n-pentyloxy, thiol, 2-methylthienyl, 3-ethylthienyl Wait.
- alkyl moiety and all fluorinated alkyl groups are substituted.
- n is a natural number between 7 and 80.
- n is a natural number between 8 and 60.
- n is a natural number between 10 and 50.
- n is a natural number between 15 and 45.
- n is 18, 20, 24, 25, 26, 27, 29, 31, 33, 35, 36, 38, 42, etc.
- the ratio of reactants and/or reaction time is controlled to control the degree of polymerization based on subsequent product applications.
- R 3 and R4 are the same; and, like, R 3 and R 4 are different; or, unlike R 4 , R 3 is the same as R 4 .
- R 3 and R 4 are each a methyl group; or, R 2 , R 3 and R 4 are both H.
- R 2 is an ethyl group
- R 2 is a pentyl group
- R 3 is H
- R 4 is a 3-methyl amidine group.
- R 2 is an n-pentyl group or an isopentyl group, that is, a linear alkyl group or a branched alkyl group, and the same applies hereinafter.
- R 2 is the same and all are propyl; R 3 is 12 alkyl; and R 4 is ethoxy.
- R 2 is a 12 alkyl group
- R 3 is a 14 alkoxy group
- R 4 is an octyl group
- Example 1 This example discloses a benzodioxin containing a pyridyl[2,l,3] p -soxadiazole unit having the following structure.
- MALDI-TOF-MS matrix-assisted laser desorption I Ionization Time of Flight Mass Spectrometry
- MALDI-TOF-MS (; m/z) is 477.0 (M+).
- oxalyl chloride on the first day For example, add 1 mL of oxalyl chloride on the first day, add 1 mL of oxalyl chloride on the third day, and add 1 mL of oxalyl chloride on the 5th day; or, add 1 mL of oxalyl chloride on the first day, and add 0.5 mL on the second day.
- Oxalyl chloride 1.5 mL of oxalyl chloride was added on the 5th day; or, 0.5 mL of oxalyl chloride was added on the first day, 1 mL of oxalyl chloride was added on the 3rd day, and 1.5 mL of oxalyl chloride was added on the 5th day.
- the temperature of the n-hexane is the same as the reaction temperature, or the temperature of the n-hexane is the reaction temperature ⁇ 5 ° C; for example, according to the molar ratio, the amount of potassium hydroxide is 5,3-bis(2-thiophene)acetone Times.
- MALDI-TOF-MS (m/z): 679.0 (M+).
- reaction was stopped after 24 h of reaction. After adding 50 mL of n-hexane to dilute, the reaction solution was slowly poured into water, and the extracted organic phase was washed with 5% NaHC0 3 , saturated NaCl solution, dried with anhydrous sulfuric acid, filtered, and then evaporated under reduced pressure. An excess of trimethyltin chloride was distilled off to obtain a product.
- the polymer solution was rotary-screwed to about 5 ml, and it was dropped into a methanol solvent and stirred for several hours. Finally, the polymer is collected and dried. The polymer is extracted with a Soxhlet extractor to increase the monodispersity of the molecular weight of the polymer.
- Example 2 This example discloses a benzodioxin containing a pyridyl[2,l,3] p -soxadiazole unit having the following structure.
- the liquid was evaporated to about 5 ml, and it was added dropwise to 300 ml of anhydrous methanol and stirred for about 4 hours. A solid precipitated gradually, and after filtration and drying, a solid powder was obtained. The solid powder was dissolved in chloroform, and the column was passed through a neutral alumina column to remove the catalyst Pd 2 (dba) 3 . Finally, the polymer solution was rotary-screwed to about 5 ml, and it was dropped into a methanol solvent and stirred for several hours. Finally, the polymer is collected and dried. The polymer is extracted with a Soxhlet extractor to increase the monodispersity of the molecular weight of the polymer.
- Example 3 This example discloses a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit as follows:
- Example 4 This example discloses a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit as follows:
- the catalyst was quickly added with 0.046 mg, 0.00005 mmoK 0.01% mol of Pd 2 (dba) 3 and 0.0304 mg, 0.0001 mmol of P(o-Tol) 3 to the reaction flask, wherein the molar ratio of Pd 2 (dba) 3 to P(o-Tol) 3 is 1:2.
- the mixture was heated to reflux at 120 ° C, and the reaction was stirred for 48 h.
- reaction solution was cooled to room temperature, and the reaction liquid was evaporated to about 5 ml by distillation under reduced pressure, and the mixture was added dropwise to 300 ml of anhydrous methanol and stirred for about 4 hours, and a solid precipitate was gradually formed.
- a solid powder is obtained.
- the solid powder was dissolved in chloroform, and the column was passed through a neutral alumina column to remove the catalyst Pd 2 (dba) 3 .
- the polymer solution was rotary-screwed to about 5 ml, and it was dropped into a methanol solvent and stirred for several hours. , Finally the polymer is collected and dried.
- Example 5 discloses a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit as follows:
- the polymer solution was rotary evaporated to about 5 ml, which was dropped into a methanol solvent and stirred for several hours. Finally, the polymer is collected and dried. The polymer is extracted by a Soxhlet extractor to increase the monodispersity of the molecular weight of the polymer.
- the polymer solution was rotary evaporated to about 5 ml, which was dropped into a methanol solvent and stirred. After a few hours, the polymer is finally collected and dried. The polymer is extracted with a Soxhlet extractor to increase the monodispersity of the molecular weight of the polymer.
- reaction mixture was stirred with nitrogen for 15 min, and then the catalyst 11.6 mg, 0.01 mmol, 2% mol of tetrakistriphenylphosphorus palladium was quickly added to the reaction flask.
- the mixture was heated to reflux at 110 ° C, and the reaction was stirred for 24 h.
- the reaction solution was cooled to room temperature, and the reaction liquid was evaporated to about 5 ml by distillation under reduced pressure.
- the mixture was added dropwise to 300 ml of anhydrous methanol and stirred for about 4 hours, and a solid precipitated gradually.
- Example 8 This example discloses a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit as follows:
- reaction solution was cooled to room temperature, and the reaction liquid was evaporated to about 5 ml by distillation under reduced pressure.
- the mixture was added dropwise to 300 ml of anhydrous methanol and stirred for about 4 h.
- precipitation after suction filtration and drying, a solid powder is obtained.
- the solid powder was dissolved in chloroform, and the catalyst was passed through a neutral alumina column to remove the catalyst tetrakistriphenylphosphorus palladium.
- the polymer solution was rotary evaporated to about 5 ml, which was dropped into a methanol solvent and stirred for several hours. Finally, the polymer is collected and dried. The polymer is extracted with a Soxhlet extractor to increase the monodispersity of the molecular weight of the polymer.
- the present invention also provides a benzobisthiophene copolymer containing a pyrido[2,1,3]thiadiazole unit provided in any of the above embodiments in a polymer solar cell, a polymer organic electroluminescence, Polymers are used in organic field effect transistors, polymer organic optical storage, polymer organic nonlinear materials or polymer organic lasers. Several specific embodiments are given below.
- Embodiment 9 is an organic solar cell device having the copolymer of the above Example 1, that is, a benzodithiophene copolymer containing a pyrido[2,1,3]thiadiazole unit, as an active layer material, and has a structure such as Figure 1 shows.
- the device structure is glass/ITO/PEDOT:PSS/active layer/A1, wherein ITO (indium tin oxide) is indium tin oxide with a sheet resistance of 10-20 ⁇ / ⁇ , PEDOT is poly(3) , 4-ethylenedioxythiophene), PSS is poly(styrenesulfonic acid); ITO glass is ultrasonically cleaned, treated with oxygen-Plasma, and coated with ITO on PEDOT:PSS, copolymerization of the above Example 1.
- metal aluminum electrode is prepared by vacuum evaporation technology to obtain an organic solar cell device.
- Example 10 an organic electroluminescent device comprising the copolymer of the above Example 2, that is, a benzodithiophene-based copolymer containing a pyrido[2,1,3]thiadiazole unit, is a light-emitting layer material, and its structure as shown in picture 2.
- ITO/copolymer of the invention/LiF/Al depositing a layer of indium tin oxide (ITO) having a sheet resistance of 10-20 ⁇ / ⁇ on a glass substrate as a transparent anode
- ITO indium tin oxide
- a layer of the copolymer of the above Example 2 was prepared on ITO as a light-emitting layer, and LiF was vacuum-deposited on the light-emitting layer to serve as a buffer layer, and finally metal A1 was vapor-deposited as a cathode of the device.
- an organic field effect transistor having a copolymer containing the above-mentioned Example 3, that is, a benzodithiophene-based copolymer containing a pyrido[2,1,3]thiadiazole unit, is an organic semiconductor material, and has a structure such as Figure 3 shows.
- a highly doped silicon wafer (Si) is used as a substrate, a 450 nm thick SiO 2 is used as an insulating layer, and a source electrode (S) and a drain electrode (D) are each doped with gold as an electrode.
- the copolymer of the above Example 3 was spin-coated with an organic semiconductor layer onto octadecyltrichlorosilane (OTS) modified SiO 2 .
- OTS octadecyltrichlorosilane
- the Applicant believes that those skilled in the art, in light of the present disclosure, are sufficient to understand how the invention can be practiced, and that it is sufficient to determine that the effect can be implemented and achieved within the scope defined by the claims.
- the benzodithiophene-based copolymer containing the pyrido[2,1,3]thiadiazole unit of each of the above examples can be used for each of the above applications.
Abstract
本发明涉及一种含吡啶并［2,1,3］噻二唑单元的苯并二噻吩类共聚物及其制备方法与应用，该聚合物具有结构式(I)。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的烷氧基或C1至C16烷基取代的噻吩基；X为N并且Y为CH，或者X为CH并且Y为N；n为7至80之间的一自然数。以及，该含吡啶并［2,1,3］噻二唑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。
Description
说明书 发明名称： 含吡啶并 [2,1,3】噻二唑单元的苯并二噻吩类共聚物及其制备方法与应用 【技术领域】
本发明涉及一种苯并二噻吩类共聚物， 尤其涉及一种含吡啶并 [2， 1，3]噻二唑单元的苯 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： ) 良好的溶解性， 有利于溶剂加工， 实现工业化生产； （b)对整个 太阳光光语有宽而强的吸收； （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语将是研究的重点。 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吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类共聚物，是苯 并二噻吩类单体与吡啶并 [2， 1,3]噻二唑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吡啶并 [2，1，3]噻二唑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吡啶并 [2，1，3]噻二唑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， 一种含吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类共聚物， 其 具有以下结构：
其中， 、 R2分别选自 H或〔！至 ^的烷基； R3、 R4分别选自 11、 〔！至 ^的烷基、 Ci至 C16烷氧基或 d至 C16烷基取代的噻喻基； X为 N并且 Y为 CH, 或者 X为 CH并且 Y为 N; n为 7至 80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或支链烷基， 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 8至 60之间的一自然数。
所述的苯并二噻吩类共聚物中， 与 R2相同， 和 /或， R3与 R4相同。
所述的苯并二噻吩类共聚物中， 、 R2、 R3、 R4选自以下一种组合： 与 为11, R3 与 R4为甲基； 或者， Ri、 R2、 R3、 R4均为 H; 或者， 为乙基， R2为戊基， R3为 H, R4 为 3-甲基 p塞喻基； 或者， 、 R2相同， 均为丙基； R3为 12烷基； R4为乙氧基； 或者， 为丁基， R2为 12烷基， R3为 14烷氧基， R4为辛基； 或者， 、 R2相同， 均为 H; R3为辛 氧基； R4为 H; 或者， 为己基； R2为 H; R3为 2-甲基噻喻基； R4为 H; 或者， 为 16 烷基； R2为 H; R3为甲氧基； R4为 H; 或者， 为 R2为甲基； R3为 16烷氧基； R4为 H; 或者， 、 R2相同， 均为甲基； R3为 16烷氧基； R4为 H; 或者， 、 R2相同， 均为 H; R3为己基； R4为 H; 或者， 、 R2相同， 均为 H; R3为甲基； R4为 H; 或者， 、 R2相 同， 均为 H; R3、 R4相同， 均为 H。
本发明的又一个技术方案是，一种含吡啶并 [2，1，3]噻二唑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：
其中， 、 R2分别选自 H或〔！至 ^的烷基； R3、 R4分别选自 11、 〔！至 ^的烷基、 Ci至 C16烷氧基或 d至 C16烷基取代的噻喻基； X为 N并且 Y为 CH, 或者 X为 CH并且 Y为 N; n为 7至 80之间的一自然数； 其中， Ml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°C 至 120 °C , 反应时间为 12至 72小时。
所述的制备方法中， 釆用以下步骤合成 Ml:
Sl、 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 ^口下：
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°C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 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°C , 緩慢加入 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°C 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 Ml ; 其反应
所述的制备方法中， 与 相同， 和 /或， R3与 R4相同； 或者， 、 R2、 R3、 R4选自 以下一种组合： 与 为 R3与 R4为甲基； 或者， Ri、 R2、 R3、 R4均为 H; 或者， 为乙基， R2为戊基， R3为 H, R4为 3-甲基噻喻基； 或者， 、 R2相同， 均为丙基； R3为 12烷基； R4为乙氧基； 或者， 为丁基， R2为 12烷基， R3为 14烷氧基， R4为辛基； 或 者， 、 R2相同， 均为 H; R3为辛氧基； R4为 H; 或者， 为己基； R2为 H; R3为 2-甲 基噻喻基； R4为 H; 或者， 为 16烷基； R2为 H; R3为甲氧基； R4为 H; 或者， 为 H;
R2为甲基； R3为 16烷氧基； R4为 H; 或者， 、 R2相同， 均为甲基； R3为 16烷氧基； R4为 H; 或者， 、 R2相同， 均为 H; R3为己基； R4为 H; ; 或者， 、 R2相同， 均为 H; R3为甲基； R4为 H; 或者， 、 R2相同， 均为 H; R3、 R4相同， 均为 H。
本发明的又一个技术方案是，一种釆用了任一上述的含吡啶并 [2，1，3]噻二唑单元的苯并 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， 本发明釆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。 本发明釆用苯并二噻吩类衍生物， 两个噻喻通 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 ρ塞喻类单体 Ml ,吡啶并 [2， 1，3]噻二唑类单体 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 p塞喻类单体 Ml是一种优异的给体材料， 吡啶并 [2，1，3]噻二唑类单体 M2是 一种非常优异的受体材料， 由单体 Ml、 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.本发明釆取的 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吡啶并 [2，1，3]噻二唑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， 并在噻喻上的 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吡 啶并 [2，1，3]噻二唑共聚， 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，所述的一种含吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类共聚物具有以下结 构：
上式中， 、 R2相同或不同， 、 R2为 H或 至〔16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 C!至 C16的烷基、 d 至 C16烷氧基、 或者 d至 C16烷基取代的噻喻基； X为 N并且 Y为 CH, 或者 X为 CH并 且 Y为 N; n为 8至 60之间的自然数。
又一个例子是，一种制备上述含吡啶并 [2， l，3]p塞二唑单元的苯并二噻吩类共聚物的制备 方法， 其制备方法如下：
其中， 如上述结构图所示， M2为 4， 7-二溴 -[1，2，5]噻二唑 [3， 4-c]吡啶， 其制备方法为现 有技术。 又如， M2中， 釆用氯替代溴。
优选的， 在无氧的环境下， 将上述两种原料 Ml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， 、 R2分别选自 H或 至 的烷基； 例如， 、 R2分别选自 H或 至〔16 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 11、 至 ^的烷基、 至 C16烷氧基或 至 C16烷基取代的噻喻基； 例如， R3、 R4分别选自 H、 至 C16的直链烷基或支链烷基、 至 C16直链烷氧基或支链 烷氧基， 或 至 C16的直链烷基或支链烷基取代的噻喻基， 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、 噻喻基、 2-甲基噻喻基、 3-乙基噻 喻基等。
X为 N时 Y为 CH, 或者 X为 CH时 Y为 N; n为 7至 80之间的一自然数； 例如， n 为 8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 Μ2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。 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°C ~ 120°C, 反应时间为 12〜72h。 例如， 反应温度为 61°C、 65 V、 72°C、 78°C、 80.5°C、 87°C、 91°C、 105°C或 119°C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 Ml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 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、 9小时、 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°C 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 12 min, 优选 10 min, 得到产物， 即化合物 D; 其中， 溶剂为乙醇、 丙醇等， 其反
D 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°C进行回流反应， 例如， 均 匀加热至 80°C、 85 °C、 90°C、 91 °C、 96°C或者 99°C进行回流反应； 在加热前、 加热过程 中或者加热达到 78°C以上时， 加入还原剂； 优选的， 加热达到 78 °C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 °C , 緩慢加入 n-BuLi (正丁基裡） 的正己烷溶液， 摩尔比为 n-BuLi： D = 1 ： 2.5 , 加毕， 在 -78°C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
上述各例中， 与 相同， 并且 R3与 R4相同； 又如， 与 相同， R3与 R4不相同； 或者， 与 不相同， R3与 R4相同。 又如， 、 R2、 R3、 R4选自以下一种组合： Ri与 R2为 H, R3与 R4为甲基； 或者， Ri、 R2、 R3、 R4均为 H; 或者， 为乙基， R2为戊基，
R3为 H, R4为 3-甲基噻喻基； 或者， 、 R2相同， 均为丙基； R3为 12烷基； R4为乙氧基； 或者， 为丁基， R2为 12烷基， R3为 14烷氧基， R4为辛基； 或者， 、 R2相同， 均为 H; R3为辛氧基； R4为 H; 或者， 为己基； R2为 H; R3为 2-甲基噻喻基； R4为 H; 或者， Ri为 16烷基； R2为 H; R3为甲氧基； R4为 H; 或者， 为 H; R2为甲基； R3为 16烷氧 基； R4为 H; 或者， 、 R2相同， 均为甲基； R3为 16烷氧基； R4为 H; 或者， 、 R2相 同， 均为 H; R3为己基； R4为 H; 或者， 、 R2相同， 均为 H; R3为甲基； R4为 H; 或者， 、 R2相同， 均为 H; R3、 R4相同， 均为 H。
例如， 所述含吡啶并 [2， 1， 具有以下结构：
上式中： 、 R2相同或不同地表示为 H或 至 的烷基， R3、 R4相同或者不同地表 示为 d至 C16的烷基， Ci至 C16烷氧基， 或者 d至 C16烷基取代的噻喻基； X为 N并且 Y 为 CH, 或者 X为 CH并且 Y为 N; n = 8-60之间的自然数。
例如， 、 R2分别选自 H或 C!至 C16的烷基； 例如， 、 R2分别选自 H或 C!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 11、 至 ^的烷基、 至 C16烷氧基或 至 C16烷基取代的噻喻基； 例如， R3、 R4分别选自 H、 至 C16的直链烷基或支链烷基、 至 C16直链烷氧基或支链 烷氧基， 或 至 C16直链烷基或支链烷基取代的噻喻基， 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、 噻喻基、 2-甲基噻喻基、 3-乙基噻吩 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。
n为 7至 80之间的一自然数， 例如， n为 8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， 与 相同， 并且 R3与 R4相同； 又如， 与 相同， R3与 R4不相同； 或者， 与 不相同， R3与 R4相同。
又如， 所述的苯并二噻吩类共聚物中， 与 为 R3与 R4为甲基； 或者， 、 R2、 R3、 R4均为 H。
例如， 为乙基； R2为戊基； R3为 H; R4为 3-甲基瘗喻基。 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， 、 R2相同， 均为丙基； R3为 12烷基； R4为乙氧基。
又如， 为丁基， R2为 12烷基， R3为 14烷氧基， R4为辛基。
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吡啶并 [2，l，3]p塞二唑单元的苯并二瘗喻类共
其中， 、 R2相同， 均为 H; R3为辛氧基； R4为 H; X为 N时 Y为 CH, 或者 X为 CH时 Y为 N; n = 60。
上述含吡啶并 [2， 1，3]噻二唑单元的苯并二噻喻类共聚物的制备步骤如下：
一、 1,3-二 (2-噻喻)丙酮的制备：
首先，用无水处理过的 70 mL二氯甲烷将 7.6 g、36.8 mmol的 DCC, 1.23g、 10 mmol的 DMAP 溶解， 在氮气保护下， 将溶有 5 g、 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语， Matrix-Assisted Laser Desorption I Ionization Time of Flight Mass Spectrometry )质荷 t匕 (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 [l， ，]二噻吩 -4 , 5-二酮的制备：
取 25.4 g (60 mmol) 4， 4'-二 (2-辛氧基)噻喻力。入至干燥的 400 mL 1 ,2-二氯乙烷中， 再将 3 mL ( 34.5 mmol ) 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， 在水箱里冷冻过夜， 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 1 mL乙二酰氯， 第 3天加入 1 mL乙二酰氯， 第 5天加入 1 mL乙二酰氯； 或者， 第 1天加入 1 mL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 0.5 mL乙二酰氯， 第 3天加入 1 mL乙二酰氯， 第 5天加入 1.5 mL乙二酰氯。
三、 2,5-二辛氧基 -7,9-二2-噻喻) -8H-环戊二烯苯并 [l，2-b:4，3-b，]二噻吩 -8-酮的制备：
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 [l，2-b:4，3-b，]二噻吩 -8-酮的制备：
MALDI-TOF-MS (m/z): 1004.6 (M+).
五、 含吡啶并 [2， 二唑单元的苯并二噻喻类共聚物的制备：
在氮气保护下， 将 0.5g、 0.5 mmol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 [l，2-b:4，3-b，]二噻吩 -8-酮和 0.15g、 0.5 mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3， 4-c]吡啶（如 上述反应式的对应结构式所示， 下同）加入至盛有 10 mL干燥甲苯的反应瓶中， 反应混合物 通氮气搅拌 15 min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)323 mg，
0.025 mmol, 5% mol; P(o-Tol)3152 mg, 0.5 mmol; Pd2(dba)3 与 P(o-Tol)3摩尔比为 1 : 20。
通氮气室温搅拌 15 min后， 加热至 80°C回流， 搅拌反应 72 h。 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 5 ml左右，将其滴入到 300 ml无水甲醇中不断搅 拌约 4h^， 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。
釆用凝胶渗透色语（GPC, Gel Permeation Chromatography ) 法测量分子量， GPC: Mn = 47760, 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吡啶并 [2，l，3]p塞二唑单元的苯并二瘗喻类共
其中， 为己基； R2为 H; R3为 2-甲基噻喻基； R4为 H; X为 N并且 Y为 CH, 或 者 X为 CH并且 Y为 N; n = 55。
上述含吡啶并 [2， 1，3]噻二唑单元的苯并二噻喻类共聚物的制备步骤如下：
一、 二（4-二己基 -2-噻吩）
首先， 用无水处理过的 70 mL二氯甲烷将 7.6 g DCC, 1.23 g DMAP溶解， 在氮气条件下, 将溶有 7.6 g 4-己基 -2-噻吩乙酸的 60 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 (m/z): 391 (M+).
二、 2， 7-二（2-甲基 -5-噻吩）苯并 [l，2-b:4，3-b，]二噻吩 -4, 5-二酮的制备：
取 21.5 g、 60 mmol的 4， 4'-二 [2- ( 2-甲基 -5-噻吩） ]噻喻力。入至 350 mL干燥的 1,2-二氯乙 烷中， 再将 3 mL、 34.5 mmol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 15 day。 反应结束后， 将反应液冷却至室温， 在水箱里冷冻过夜， 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-噻喻) -7,9-二 (4-己基 -2-噻喻) -8H-环戊二烯苯并 [l，2-b:4，3-b，]二噻吩 -8-酮的制备：
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 [l，2-b:4，3-b']二噻吩 -8-酮的制备：
在氮气保护下，将 7.65g、 lOmmol的的 2,5-二 (2-甲基 -5-噻喻) -7,9-二 (4-己基 -2-噻喻) -8H- 环戊二烯苯并 [l，2-b:4，3-b，]二噻吩 -8-酮和 150 mL无水 THF冷却至 -78 °C , 緩慢加入 5 mL、 12 mmol的正丁基锂的正己烷溶液（2.5 M )。 加毕， 在 -78 °C下保温反应 2 h后加入 4.5 mL、 15 mmol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 50 mL正己烷稀释，反应液緩慢倒入到水水中，萃取得到的有机相分别用 5%的 NaHC03， 饱和 NaCl溶液水洗， 无水硫酸键干燥， 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、 含吡啶并 [2， 1，3]
在氮气保护下， 将 0.82g、 0.75 mmol的 2,5-二 (2-甲基 -5-噻喻) -7,9-二 (4-己基 -2-三甲基锡 -5- 噻喻) -8H-环戊二烯苯并 [l，2-b:4，3-b']二噻吩 -8-酮和 0.15g、 0.5 mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3， 4-c]吡啶加入至盛有 lO mL干燥四氢呋喃的反应瓶中， 即加入至盛有 10 mL无水四氢呋喃的反 应瓶中或加入至盛有 10 mL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 15 min 后，迅速加入催化剂 14 mg、 0.015 mmoK 3% mol的 Pd2(dba)3和 68 mg、 0.225 mmol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 15 min后， 加热至 60 °C下回流， 搅拌反应 60 h。 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 5 ml左右， 将其滴入到 300 ml无水甲醇中不断搅拌约 4h^， 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 = 49500, PDI = 1.8。 实施例 3、 本实施例公开一种结构如下的含吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类 共聚物：
其中， 为 16烷基； R2为 H; R3为甲氧基； R4为 H; X为 N并且 Y为 CH, 或者 X 为 CH并且 Y为 N; 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 [l，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、 含吡啶并 [2， 1，3]噻二唑单元的苯并二噻喻类共聚物的制备:
在氮气保护下， 将 0.74 g、 0.6 mmol的 2,5-二甲氧基苯 -7,9-二 (4-十六烷基 -5-三甲基锡 -2- 噻喻) -8H-环戊二烯苯并 [l，2-b:4，3-b']二噻吩 -8-酮和 0.15g、 0.5 mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3, 4-c]吡啶加入至盛有 lO mL干燥 DMF的反应瓶中， 反应混合物通氮气搅拌 15 min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)30.046 mg， 0.00005 mmol, 0.01% mol; P(o-Tol)30.0304 mg, 0.0001 mmol; Pd2(dba)3 与 P(o-Tol)3摩尔比为 1 : 2。 通氮气室温搅拌 15 min 后， 加热至 120 °C回流， 搅拌反应 48 h。 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 5 ml左右，将其滴入到 300 ml无水甲醇中不断搅拌约 4h^，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 = 36715 , PDI = 1.8。 实施例 4、 本实施例公开一种结构如下的含吡啶并 [2,1,3]噻二唑单元的苯并二噻吩类 共聚物：
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 [l，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、 含吡啶 [2， 1，3]噻二唑单元的苯并二噻喻类共聚物的制备:
在氮气保护下， 将 0.62 g、 0.5 mmol的 2,5-二（十六烷氧基） -7,9-二 (3-甲基 -5-三甲基锡 -2- 噻喻) -8H-环戊二烯苯并 [l，2-b:4，3-b']二噻吩 -8-酮和 0.15g、 0.5 mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3, 4-c]吡啶加入至盛有 lO mL干燥 DMF的反应瓶中， 反应混合物通氮气搅拌 15 min后， 迅速加 入催化剂 0.046 mg、 0.00005 mmoK 0.01% mol的 Pd2(dba)3和 0.0304 mg、 0.0001 mmol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 15 min后， 加热至 120 °C回流， 搅拌反应 48 h。 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 5 ml左右， 将其滴入到 300 ml无水甲醇中不断搅拌约 4h^， 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 c GPC: Mn = 31470, PDI = 1.8。 实施例 5、 本实施例公开一种结构如下的含吡啶并 [2,1 ,3]噻二唑单元的苯并二噻吩类 共聚物：
其中， 、 R2相同， 均为甲基； R3为 16烷氧基； R4为 H; X为 N并且 Y为 CH, 或 者 X为 CH并且 Y为 N; n = 20。
一、 2,5-二 （十六烷基） -7,9-二 (3, 4-二曱基 -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): 1237 (M+).
二、 含吡啶并 [2,1,3]噻二唑单元的苯并二噻吩类共聚物的制备:
在氮气保护下， 将 0.62 g、 0.5 mmol的 2,5-二（十六烷基） -7,9-二 (3， 4-二甲基 -5-三甲基锡 -2-噻喻) -8H-环戊二烯苯并 [l，2-b:4，3-b']二噻吩 -8-酮和 0.15g、 0.5 mmol的 4， 7-二溴 -[1，2，5]噻二 唑 [3， 4-c]吡啶加入至盛有 10 mL干燥苯的反应瓶中， 反应混合物通氮气搅拌 15 min后， 迅速 加入催化剂 28.9 mg， 0. 025 mmol, 5% mo 1的四三苯基磷钯至反应瓶中。 通氮气室温搅拌 15 min 后， 加热至 80°C下回流， 搅拌反应 24 h。 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 5 ml左右，将其滴入到 300 ml无水甲醇中不断搅拌约 4h^，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 = 20900, PDI = 2.2。 实施例 6、 本实施例公开一种结构如下的含吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类 共聚物：
一、 2,5-二己基 -7,9-二 (5-三甲基锡 -2-噻喻) -8H-环戊二烯苯并 [l，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、 含吡啶并 [2
在氮气保护下， 将 0.45g、 0.5 mmol的 2,5-二己基 -7,9-二 (5-三甲基锡 -2-噻喻) -8H-环戊二烯 苯并 [l，2-b:4，3-b，]二噻吩 -8-酮和 0.15g、 0.5mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3， 4-c]吡啶加入至盛 有 10 mL干燥甲苯的反应瓶中， 反应混合物通氮气搅拌 15 min后， 迅速加入催化剂 3.5 mg， 0.005 mmol, 1% mol 的 Pd(PPh3)2Cl2至反应瓶中。通氮气室温搅拌 15 min后，加热至 110 °C下回 流， 搅拌反应 24 h。 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 5 ml左右，将其滴入到 300 ml无水甲醇中不断搅拌约 4h^，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 = 10620 , PDI = 2.2。
实施例 本实施例公开一种结构如下的含吡啶并 [2， 1，3]噻二唑单元的苯并二噻吩类 共聚物：
其中， 、 R2相同， 均为 H; R3为甲基； R4为 H; X为 N并且 Y为 CH, 或者 X为 CH并且 Y为 N; n = 10。
一、 2,5-二甲基 -7,9-二 (5-三甲基锡 -2-噻喻) -8H-环戊二烯苯并 [l，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、 含吡啶并 [2， 1，3]噻二唑单元的苯并二噻喻类共聚物的制备:
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-噻喻) -8H-环戊二烯 苯并 [l，2-b:4，3-b，]二噻吩 -8-酮和 0.15g、 0.5mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3， 4-c]吡啶加入至盛
有 10mL干燥甲苯的反应瓶中，反应混合物通氮气搅拌 15 min后，迅速加入催化剂 11.6 mg、 0.01 mmol、 2% mol的四三苯基磷钯至反应瓶中。 通氮气室温搅拌 15 min后， 加热至 110°C下回流， 搅拌反应 24 h。 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 5 ml 左右， 将其滴入到 300 ml无水甲醇中不断搅拌约 4h^， 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 = 5680, PDI = 2.2。 实施例 8、 本实施例公开一种结构如下的含吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类 共聚物：
其中， 、 R2相同， 均为 H; R3、 R4相同， 均为 H; n = 8。
一、 7,9-二 (5-三甲基锡 -2-噻喻 -8H-环戊二烯苯并 [l，2-b:4，3-b，]二噻吩 -8-酮的制备:
MALDI-TOF-MS (m/z): 732 (M+).
二、 含吡啶并 [2， 1，3]噻二唑单元的苯并二噻喻类共聚物的制备:
在氮气保护下， 将 0.37g、 0.5 mmol的 7,9-二 (5-三甲基锡 -2-噻喻) -8H-环戊二烯苯并
[l，2-b:4，3-b，]二噻吩 -8-酮和 0.15g、 0.5 mmol的 4， 7-二溴 -[1，2，5]噻二唑 [3， 4-c]吡啶加入至盛有 10 mL干燥苯的反应瓶中， 反应混合物通氮气搅拌 15 min后， 迅速加入催化剂 0.29 mg、 0.00025 mmol、 0.05% mol的四三苯基磷钯至反应瓶中。通氮气室温搅拌 15 min后，加热至 80°C下回流， 搅拌反应 12 h。 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 5 ml 左右， 将其滴入到 300 ml无水甲醇中不断搅拌约 4 h^ , 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 = 4320, PDI = 2.3。 并且，本发明还提供了上述任一实施例所提供的含吡啶并 [2，1，3]噻二唑单元的苯并二噻 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， 即含吡啶并 [2,1,3]噻二唑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 /A1, 其中 ITO (氧化铟锡）是方块电阻为 10-20 Ω/口的氧化铟锡， PEDOT为聚 (3,4-亚乙二氧基噻喻)， 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作为电子受体材料釆用旋
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， 即含吡啶并 [2，1，3]噻二唑单元的苯并二噻 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。
有机电致发光器件的制备： 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 10-20 Ω/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, 作为緩冲层， 最 后蒸镀金属 A1, 作为器件的阴极。
实施例 11、 对含有上述实施例 3的共聚物， 即含吡啶并 [2，1，3]噻二唑单元的苯并二噻 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： 釆用高掺杂的硅片 （Si )作为衬底， 450 nm厚的 Si02作为 绝缘层， 源电极（S ) , 漏电极（D ) 均釆用金作为电极， 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 Si02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吡啶并 [2，1，3]噻二唑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
权利要求书 一种含吡啶并 [2，l，3]p塞二唑单元的苯并二瘗喻类共聚物， 其特征在于， 具有以
其中， 、 R2分别选自 H或 至 的烷基；
R3、 R4分别选自 11、 至 ^的烷基、 至 C16烷氧基或 至 C16烷基取代的噻喻基； X为 N并且 Y为 CH, 或者 X为 CH并且 Y为 N;
n为 7至 80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 基或支链烷基， 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 8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， 与 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， 、 R2、 R3、 R4选 自以下一种组合：
与 为 R3与 R4为甲基； 或者，
、 R2、 R3、 R4均为 H; 或者，
为乙基， R2为戊基， R3为 H, R4为 3-甲基噻喻基； 或者，
、 R2相同， 均为丙基； R3为 12烷基； R4为乙氧基； 或者，
Ri为丁基， R2为 12烷基， R3为 14烷氧基， R4为辛基； 或者，
、 R2相同， 均为 H; R3为辛氧基； R4为 H; 或者，
Ri为己基； R2为 H; R3为 2-甲基噻喻基； R4为 H; 或者，
Ri为 16烷基； R2为 H; R3为甲氧基； R4为 H; 或者，
为 R2为甲基； R3为 16烷氧基； R4为 H; 或者，
、 R2相同， 均为甲基； R3为 16烷氧基； R4为 H; 或者，
、 R2相同， 均为 H; R3为己基； R4为 H; 或者，
、 R2相同， 均为 H; R3为甲基； R4为 H; 或者，
、 R2相同， 均为 H; R3、 R4相同， 均为 H。
6、 一种含吡啶并 [2，1，3]噻二唑单元的苯并二噻吩类共聚物的制备方法， 其特征在 包括以下步骤，
在无氧的环境下， 将以下两种原料：
其中， 、 R2分别选自 H或 至 的烷基；
R3、 R4分别选自 11、 至 ^的烷基、 至 C16烷氧基或 至 C16烷基取代的噻喻基;
X为 N并且 Y为 CH, 或者 X为 CH并且 Y为 N;
n为 7至 80之间的一自然数；
其中， Ml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°C至 120°C , 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， 釆用以下步骤合成 Ml :
Sl、 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°C进行回流反应， 再加入还原剂， 再继续反应 10分钟， 得到化合物 D; 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；
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°C , 緩慢加入 含有正丁基裡的正己烷溶液， 其中， 正丁基锂与 D的摩尔比为 1 :2.5 , 然后在 -78°C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 Ml ; 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或支链烷 基， 所述烷氧基为直链烷氧基或支链烷氧基； 并且， n为 8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， 与 R2相同， 和 /或， R3与 R4 相同； 或者， 、 R2、 R3、 R4选自以下一种组合：
与 为 R3与 R4为甲基； 或者，
、 R2、 R3、 R4均为 H; 或者，
为乙基， R2为戊基， R3为 H, R4为 3-甲基噻喻基； 或者，
、 R2相同， 均为丙基； R3为 12烷基； R4为乙氧基； 或者，
Ri为丁基， R2为 12烷基， R3为 14烷氧基， R4为辛基； 或者，
、 R2相同， 均为 H; R3为辛氧基； R4为 H; 或者，
Ri为己基； R2为 H; R3为 2-甲基噻喻基； R4为 H; 或者，
Ri为 16烷基； R2为 H; R3为甲氧基； R4为 H; 或者，
为 R2为甲基； R3为 16烷氧基； R4为 H; 或者，
、 R2相同， 均为甲基； R3为 16烷氧基； R4为 H; 或者，
、 R2相同， 均为 H; R3为己基； R4为 H; 或者，
、 R2相同， 均为 H; R3为甲基； R4为 H; 或者，
、 R2相同， 均为 H; R3、 R4相同， 均为 H。
10、 权利要求 1至 5任一所述的含吡啶并 [2，l，3]p塞二唑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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| JP2015544298A JP6096313B2 (ja) | 2012-11-30 | 2012-11-30 | ピリジノ［２，１，３］チアジアゾールユニットを含有するベンゾジチオフェン系共重合体、製造方法、及び、その使用方法 |
| US14/646,783 US9328203B2 (en) | 2012-11-30 | 2012-11-30 | Benzodithiophene based copolymer containing pyridino [2,1,3] thiadiazole units and preparing method and applications thereof |
| PCT/CN2012/085681 WO2014082309A1 (zh) | 2012-11-30 | 2012-11-30 | 含吡啶并[2,1,3]噻二唑单元的苯并二噻吩类共聚物及其制备方法与应用 |
| EP12889016.7A EP2927257A4 (en) | 2012-11-30 | 2012-11-30 | BENZODITHIOPHASE BASE COPOLYMER WITH PYRIDINO [2,1,3] THIADIAZOL UNITS, AND METHOD OF PRODUCTION AND APPLICATIONS THEREOF |
| CN201280076703.1A CN104769003B (zh) | 2012-11-30 | 2012-11-30 | 含吡啶并[2,1,3]噻二唑单元的苯并二噻吩类共聚物及其制备方法与应用 |
| US14/647,631 US9328194B2 (en) | 2012-11-30 | 2012-12-03 | Benzodithiophene based copolymer containing isoindoline-1,3-diketone units and preparing method and applications thereof |
| PCT/CN2012/085741 WO2014082313A1 (zh) | 2012-11-30 | 2012-12-03 | 含异吲哚啉-1,3-二酮单元的苯并二噻吩类共聚物及其制备方法与应用 |
| JP2015544301A JP6096315B2 (ja) | 2012-11-30 | 2012-12-03 | イソインドリン−１，３−ジケトンユニットを含有するベンゾジチオフェン系共重合体、製造方法、及び、その使用方法 |
| EP12889159.5A EP2927260B1 (en) | 2012-11-30 | 2012-12-03 | Benzodithiophene based copolymer containing isoindoline-1,3-diketone units and preparing method and applications thereof |
| CN201280076704.6A CN104769004B (zh) | 2012-11-30 | 2012-12-03 | 含异吲哚啉-1,3-二酮单元的苯并二噻吩类共聚物及其制备方法与应用 |
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| EP (1) | EP2927257A4 (zh) |
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| CN104769002B (zh) * | 2012-11-30 | 2016-10-12 | 海洋王照明科技股份有限公司 | 含噻吩并[3,4-b]噻吩单元的苯并二噻吩类共聚物及其制备方法与应用 |
| US9837637B2 (en) * | 2014-10-16 | 2017-12-05 | National Taiwan University | Electroluminescent devices with improved optical out-coupling efficiencies |
| CN107141451B (zh) * | 2017-04-11 | 2018-07-20 | 中国石油大学(华东) | 一种聚合物太阳能电池器件光活性层用d-a型共聚物给体材料 |
| CN113214189B (zh) * | 2021-04-12 | 2023-01-24 | 南昌航空大学 | 一种共轭小分子热电材料及其制备方法 |
| CN114409682A (zh) * | 2022-02-14 | 2022-04-29 | 中国科学院化学研究所 | 具有定位效应的三氮唑并吡啶类受体、其聚合物以及它们的应用 |
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| WO2011131280A1 (en) * | 2010-04-19 | 2011-10-27 | Merck Patent Gmbh | Polymers of benzodithiophene and their use as organic semiconductors |
| WO2012031404A1 (zh) * | 2010-09-10 | 2012-03-15 | 海洋王照明科技股份有限公司 | 苯并二噻吩有机半导体材料及其制备方法和应用 |
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| US20090314997A1 (en) * | 2006-07-26 | 2009-12-24 | Martin Heeney | Substituted benzodithiophenes and benzodiselenophenes |
| TWI471328B (zh) * | 2008-07-02 | 2015-02-01 | Basf Se | 以二噻吩并〔２，３－ｄ：２’，３’－ｄ’〕苯并〔１，２－ｂ：４，５－ｂ’〕二噻吩為主之高效能溶液可加工之半導體 |
| PT2501698T (pt) * | 2009-11-18 | 2018-07-23 | Nat Res Council Canada | Monómeros fluorados, oligómeros e polímeros para utilização em dispositivos eletrónicos orgânicos |
| CN103249799B (zh) * | 2010-09-02 | 2016-07-06 | 默克专利股份有限公司 | 含新型光活性聚合物的光伏电池 |
| CN102060982B (zh) * | 2010-12-03 | 2012-08-22 | 华南理工大学 | 含萘[1,2-c:5,6-c]二[1,2,5]噻二唑的有机半导体材料及其应用 |
| JP2013237813A (ja) * | 2012-05-16 | 2013-11-28 | Kuraray Co Ltd | π電子共役重合体及びそれを用いた有機半導体デバイス |
| WO2014082310A1 (zh) * | 2012-11-30 | 2014-06-05 | 海洋王照明科技股份有限公司 | 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 |
| CN104769002B (zh) * | 2012-11-30 | 2016-10-12 | 海洋王照明科技股份有限公司 | 含噻吩并[3,4-b]噻吩单元的苯并二噻吩类共聚物及其制备方法与应用 |
| WO2014082313A1 (zh) * | 2012-11-30 | 2014-06-05 | 海洋王照明科技股份有限公司 | 含异吲哚啉-1,3-二酮单元的苯并二噻吩类共聚物及其制备方法与应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011131280A1 (en) * | 2010-04-19 | 2011-10-27 | Merck Patent Gmbh | Polymers of benzodithiophene and their use as organic semiconductors |
| WO2012031404A1 (zh) * | 2010-09-10 | 2012-03-15 | 海洋王照明科技股份有限公司 | 苯并二噻吩有机半导体材料及其制备方法和应用 |
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| See also references of EP2927257A4 * |
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| CN104769003B (zh) | 2016-10-12 |
| CN104769003A (zh) | 2015-07-08 |
| US20150284505A1 (en) | 2015-10-08 |
| JP6096313B2 (ja) | 2017-03-15 |
| US9328203B2 (en) | 2016-05-03 |
| EP2927257A4 (en) | 2016-04-13 |
| EP2927257A1 (en) | 2015-10-07 |
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