CN103923106B - Conjugated polymer that a kind of mental retardation gap length absorbs and preparation method thereof - Google Patents
Conjugated polymer that a kind of mental retardation gap length absorbs and preparation method thereof Download PDFInfo
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- CN103923106B CN103923106B CN201410179009.3A CN201410179009A CN103923106B CN 103923106 B CN103923106 B CN 103923106B CN 201410179009 A CN201410179009 A CN 201410179009A CN 103923106 B CN103923106 B CN 103923106B
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- Prior art keywords
- bis
- diazosulfide
- catalyst
- monomer
- ethylene dioxythiophene
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 208000036626 Mental retardation Diseases 0.000 title claims abstract description 16
- 229920000547 conjugated polymer Polymers 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 23
- 238000003808 methanol extraction Methods 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 18
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- 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 10
- 238000003756 stirring Methods 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- -1 wash three times Chemical compound 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- OBBQDLHBLQTARQ-UHFFFAOYSA-N hexan-1-amine;hydrate Chemical compound [OH-].CCCCCC[NH3+] OBBQDLHBLQTARQ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 2
- KIGVOJUDEQXKII-UHFFFAOYSA-N 4-bromo-n-(4-bromophenyl)-n-phenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC(Br)=CC=1)C1=CC=CC=C1 KIGVOJUDEQXKII-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 2
- YEDAAGQNVVUVGC-UHFFFAOYSA-N C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1.[Br] Chemical compound C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1.[Br] YEDAAGQNVVUVGC-UHFFFAOYSA-N 0.000 claims 1
- SXMUSCUQMMSSKP-UHFFFAOYSA-N [O].C=1C=CSC=1 Chemical compound [O].C=1C=CSC=1 SXMUSCUQMMSSKP-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 235000021050 feed intake Nutrition 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 4
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 11
- 238000004528 spin coating Methods 0.000 description 11
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000004305 biphenyl Substances 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 9
- 230000031709 bromination Effects 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000002220 fluorenes Chemical class 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 238000013086 organic photovoltaic Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 0 *C1(c2cc(Br)ccc2-c(cc2)c1cc2Br)I Chemical compound *C1(c2cc(Br)ccc2-c(cc2)c1cc2Br)I 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NSLJAYQJTGJPBW-UHFFFAOYSA-N S1C=CC2=C1C=CS2.C2=CC=CC=C2 Chemical class S1C=CC2=C1C=CS2.C2=CC=CC=C2 NSLJAYQJTGJPBW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NDNNMJBUIRIZNP-UHFFFAOYSA-N 1,3-thiazole;thiophene Chemical compound C=1C=CSC=1.C1=CSC=N1 NDNNMJBUIRIZNP-UHFFFAOYSA-N 0.000 description 1
- OXFFIMLCSVJMHA-UHFFFAOYSA-N 2,7-dibromo-9,9-dihexylfluorene Chemical class C1=C(Br)C=C2C(CCCCCC)(CCCCCC)C3=CC(Br)=CC=C3C2=C1 OXFFIMLCSVJMHA-UHFFFAOYSA-N 0.000 description 1
- OYTKXVQRRLZCDC-UHFFFAOYSA-N 2-thiophen-2-yl-1,3-thiazole Chemical compound C1=CSC(C=2SC=CN=2)=C1 OYTKXVQRRLZCDC-UHFFFAOYSA-N 0.000 description 1
- LQQKFGSPUYTIRB-UHFFFAOYSA-N 9,9-dihexylfluorene Chemical class C1=CC=C2C(CCCCCC)(CCCCCC)C3=CC=CC=C3C2=C1 LQQKFGSPUYTIRB-UHFFFAOYSA-N 0.000 description 1
- LNVCPXGHFUDDTN-UHFFFAOYSA-N B(O)(O)OB(O)O.C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound B(O)(O)OB(O)O.C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 LNVCPXGHFUDDTN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- HQJQYILBCQPYBI-UHFFFAOYSA-N Brc(cc1)ccc1-c(cc1)ccc1Br Chemical compound Brc(cc1)ccc1-c(cc1)ccc1Br HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-M ethanimidate Chemical compound CC([O-])=N DLFVBJFMPXGRIB-UHFFFAOYSA-M 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/413—Heck reactions
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Abstract
nullThe present invention relates to organic semiconductor preparing technical field，It is specially a kind of conjugative monomer polymer of mental retardation gap length absorption that can be applicable to solaode and preparation method thereof，The technical scheme is that with 3，4 ethylenedioxythiophene (EDOT) are supplied for electronic unit，2，1，3 diazosulfides (BT) are by electronic unit，Heck coupling reaction is used to be obtained novel D A type conjugative monomer EDOTBT by EDOT Yu BT，This conjugative monomer has stronger electronics push-pull effect，High molecular new polymers can be prepared by above-mentioned D A type conjugative monomer by Heck coupling reaction or Suzuki coupling reaction，These polymer have low band gaps、Wide absorption、Higher phototranstormation efficiency and the feature of good film property，Can be used as the active layer of polymer solar battery，The energy conversion efficiency of polymer solar battery can be effectively improved，Suitable popularization and application in polymer solar battery.
Description
Technical field
The present invention relates to organic semiconductor preparing technical field, a kind of low band gap that can be applicable to solaode
Wide conjugated polymer absorbed and preparation method thereof.
Background technology
In recent years, the cost of manufacture having due to polymer solar battery (PSC) is low, preparation convenient, safety and environmental protection and
The outstanding advantage of sustainable developability etc. is day by day notable, research circle for polymer solar battery research the most also
And it is more deep.In prior art, the research emphasis of organic photovoltaic battery is concentrated mainly in the problem of photoelectric transformation efficiency, for
Improving the photoelectric transformation efficiency of organic photovoltaic battery, research worker usually requires absorption spectrum and the sun of organic photovoltaic battery
Having the low band gap polymers material being mutually matched between optical emission spectroscopy, these low band gap polymers materials typically have
Following features: (1) is narrow can bandwidth be absorbed, and can capture more light quantum and improve short circuit current；(2) crystalline texture, it is simple to
Obtain higher photoelectric transformation efficiency；(3) relatively low HOMO energy level, can improve the open-circuit voltage (Voc) of polymer device；
(4) moderate lumo energy, it is simple to and between fullerene, produce the transfer of effective electric charge, improve hole mobility and fill factor, curve factor,
The maximally effective approach meeting above-mentioned requirements is exactly to introduce supplied for electronic unit (Donor) in the polymer backbone and by electronics
Unit (Acceptor) forms the polymer of D-A type structure, for by Intramolecular electron transfer, supplied for electronic can occur between electronic unit
The electronics releasability of unit and electronic structure and the property of D-A type polymer can be affected by the electronic receipt ability of electronic unit
Energy；Additionally, the polymer of D-A type can be able to carry by selecting different electron-donating groups and electron-accepting group regulation, energy level and electricity
Lotus mobility.
The achievement in research of relevant low band gap polymer of the prior art is as follows: Jiang J M et al.
(Macromolecules, 2011,44 (23): 9155-9163.) synthesized novel low-energy zone crystalline polymer PTHBO,
PBTTBO and PTTTBO, this article use the thiophene (TH) of electron rich, 2, the double thiophene (BT) of 2-and thienyl thiophene (TT) are for pushing away electricity
Subelement, with the 2 of electron deficiency, 1,3-benzo oxadiazoles for drawing electronic unit, resulting polymers shows and effective between fullerene
Electric charge transfer and make the energy balance of polymer, reduce the HOMO energy level of polymer, show good thermally-stabilised simultaneously
Property, high crystalline and wide absorption region.Zhang M et al. (Chemistry of Materials, 2011,23 (18): 4264-
4270.) polymer of four kinds of D-A type it is prepared for, with four dodecyls substituted benzene 1,4-Dithiapentalene (IDT) for pushing away electronics list
Unit, with four kinds of different groups double thienyl thiazole (BTz), double thiophene-thiazole base thiazole (TTz), double thienyl tetrazine
(TZ), double thienyl diazosulfide (DTBT) for drawing electronic unit, the copolymer of synthesis is respectively PIDT-BTz, PIDT-
TTz, PIDT-TZ and PIDT-DTBT.Wang M, LiC, Lv A, et al. (Polymer, 2012,53 (2): 324-332.) close
The polymer become is using triphenylamine as electron donor, using thieno diazosulfide as the D-A type copolymerization of electron withdraw group
Thing.
Summary of the invention
It is an object of the invention to provide a kind of D-A type conjugative monomer with stronger electronics push-pull effect and preparation thereof
The preparation of method, thus D-A type conjugative monomer has low band gaps, wide absorption, has higher phototranstormation efficiency and good film forming
Property feature high molecular new polymers and by these polymer make solaode active layer method.
The technical solution adopted for the present invention to solve the technical problems is: the D-A type conjugation that a kind of mental retardation gap length absorbs is single
Body, the structural formula of this monomer is:
Wherein, R is H, Cl, Br or I.
The preparation method of D-A type conjugative monomer that a kind of mental retardation gap length absorbs, has following steps:
(1) in reaction vessel add 3,4-ethylene dioxythiophene, 4, bromo-2,1, the 3-diazosulfide of 7-bis-, catalysis
Agent, part, weak base, then in container, add solvent, by inflated with nitrogen after reactor evacuation, it is heated to 90 DEG C, the lower reaction of stirring
12-48h；
(2), after reaction terminates, products therefrom is poured in distilled water and carries out extracting separatory with dichloromethane, wash three times,
Anhydrous magnesium sulfate is dried, and (wherein solid phase is alkali alumina, and flowing is toluene mutually: dichloromethane=1:1), sinks with methanol to cross post
3-5 time, shallow lake, vacuum drying treatment, obtain solid product and be target product 4,7-bis-(3,4-ethylene dioxythiophene)-benzo thiophene
Diazole (H-EDOTBT-H)；
(3) by the target product 4 of above-mentioned gained, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide (H-EDOTBT-
H) add N-halosuccinimides, glacial acetic acid in, then in container, add solvent, react under lucifuge ice bath stirring condition
24-48h；
(4) after reaction terminates, dissolving with 1-Methyl-2-Pyrrolidone after rotary evaporation is dry, methanol extraction, it is heavy to be recovered by filtration
Form sediment, vacuum drying treatment, obtain solid product and be target product Cl-EDOTBT-Cl, Br-EDOTBT-Br or I-EDOTBT-
I；
Wherein, 3,4-ethylene dioxythiophene is as shown in following structural formula I: 4,7-bis-bromo-2,1,3-diazosulfides are such as
Shown in structures below formula II, D-A type conjugative monomer H-EDOTBT-H is as shown in structures below formula III, and N-halo succinyl is sub-
Amine is as shown in structures below formula IV, and D-A type conjugative monomer Br-EDOTBT-Br is as shown in following structural formula V.
Further, in described step (1), 3,4-ethylene dioxythiophene and 4, the throwing of bromo-2,1, the 3-diazosulfide of 7-bis-
Material ratio is (2+x1): 1, x1For 0.1-0.5；
Catalyst is palladium catalyst, 3,4-ethylene dioxythiophene and 4, bromo-2,1, the 3-diazosulfide total amount of 7-bis-with urge
The mol ratio of agent is 1:0.003-0.1；
Part is tetrabutyl ammonium bromide, tricyclohexyl phosphine borofluoride, tricyclohexyl phosphine, three dredges butyl phosphine, triphenylphosphine
Or the one in triethylene diamine, part is 4-12:1 with the mol ratio of catalyst；
Weak base be potassium carbonate, potassium acetate, mass fraction be that the tetramethylammonium hydroxide aqueous solution of 5-50%, mass fraction are
The TBAH aqueous solution of 5-50%, mass fraction are the tetraethyl ammonium hydroxide aqueous solution of 5-50%, mass fraction
Four hexyl ammonium hydroxide aqueous solutions or quality for the TPAOH aqueous solution of 5-50%, mass fraction are 5-50% divide
Number is the one in the four octyl group ammonium hydroxide aqueous solutions of 5-50%, and alkali is 30-80:1 with the mol ratio of catalyst；
Solvent is DMF or N,N-dimethylacetamide, and its consumption is 3,4-ethylene dioxythiophene and 4,
The molar concentration of bromo-2,1, the 3-diazosulfide total amount of 7-bis-is at 0.1-0.5mol/L.
Further preferably, described catalyst is Pd (OAC)2、PdCl2Or Pd (PPh (dppf)3)4In one, 3,4-ethylenes
Dioxy thiophene and 4, bromo-2,1, the 3-diazosulfide total amount of 7-bis-is 1:0.035 with the optimum molar proportioning of catalyst.
Further, in described step (3), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfides (H-EDOTBT-H)
It is 1:(2+x with the rate of charge of N-halosuccinimides2), x2For 0.1-5；
Glacial acetic acid and 4, the mol ratio of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide (H-EDOTBT-H) is 9:1；
Solvent is chloroform or oxolane, and its consumption is 4,7-bis-(3,4-ethylene dioxythiophene)-2,1,3-benzo thiophene two
The molar concentration of azoles (H-EDOTBT-H) and N-halosuccinimides NBS total amount is at 0.1-5mol/L.
The polymer of the D-A type conjugative monomer that a kind of mental retardation gap length absorbs, the structural formula of this polymer is:
The number-average molecular weight of polymer is
1000-100000；
Wherein, n is 1-10；X is 0.05-0.95；R3For H, Br or
Ar is
OrIn one, R1, R2For H or (CH2)zCH3, wherein z number is 1-11.
The preparation method of the polymer of a kind of D-A type conjugative monomer containing the absorption of mental retardation gap length, can pass through two kinds of idols
Conjunction is synthesized, and a kind of method is by Heck coupling reaction, and another kind of method is by Suzuki coupling reaction.
By the conjugated polymer of Heck coupling reaction synthesis D-A type low band gap, there are following steps:
(1) in reaction vessel, 4 are added, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (H-EDOTBT-
H), 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, the one in 4 '-dibromo triphenylamine, catalysis
Agent, part, weak base, then in container, add solvent, by inflated with nitrogen after reaction vessel evacuation, it is heated to 95 DEG C, stirring condition
Lower reaction 12-48h；
(2) reaction terminate after, products therefrom is sequentially added into methanol extraction, be recovered by filtration precipitation, dichloromethane dissolve sink
Shallow lake thing, cross post (wherein solid phase is silica gel, and flowing is mutually for dichloromethane), Rotary Evaporators evaporation and concentration, add methanol extraction,
Precipitation, vacuum drying treatment are recovered by filtration, finally give solid product and be target product；
Wherein, 2,7-dibromo fluorenes, Isosorbide-5-Nitrae-dibromobenzene, 4,4 '-two bromo-1,1 '-biphenyl, 4,4 '-dibromo triphenylamine is the most such as
Below shown in VI, VII, VIII, Ⅸ structural formula, wherein R1, R2For H or (CH2)zCH3, wherein z number is 1-11,
Further, in described step (1), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (H-
EDOTBT-H) with 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, in 4 '-dibromo triphenylamine
The molar feed ratio planted is 0.5-1:1；
Catalyst is palladium catalyst, 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfides monomer (H-EDOTBT-H)
With 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, a kind of total amount in 4 '-dibromo triphenylamine
It is 1:0.003-0.1 with the mol ratio of catalyst；
Part is tetrabutyl ammonium bromide, tricyclohexyl phosphine borofluoride, tricyclohexyl phosphine, three dredges butyl phosphine, triphenylphosphine
Or the one in triethylene diamine, part is 4-12:1 with the mol ratio of catalyst；
Weak base be potassium carbonate, potassium acetate, mass fraction be that the tetramethylammonium hydroxide aqueous solution of 5-50%, mass fraction are
The TBAH aqueous solution of 5-50%, mass fraction are the tetraethyl ammonium hydroxide aqueous solution of 5-50%, mass fraction
Four hexyl ammonium hydroxide aqueous solutions or quality for the TPAOH aqueous solution of 5-50%, mass fraction are 5-50% divide
Number is the one in the four octyl group ammonium hydroxide aqueous solutions of 5-50%, alkali and 4,7-bis-(3,4-ethylene dioxythiophene)-benzo thiophene
Diazole monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, in 4 '-dibromo triphenylamine
The mol ratio of the total amount planted is 4-12:1；
Solvent is DMF, N,N-dimethylacetamide, and its consumption is 4,7-bis-(3,4-enedioxy thiophenes
Fen)-diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4,4 '-dibromo three
The molar concentration of a kind of total amount in aniline is at 0.1-0.5mol/L.
Further preferably, described catalyst is Pd (OAC)2、PdCl2Or Pd (PPh (dppf)3)4In one, 4,7-bis-
(3,4-ethylene dioxythiophene)-diazosulfide monomer (H-EDOTBT-H) and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-
Two bromo-1,1 '-biphenyl or 4, a kind of total amount in 4 '-dibromo triphenylamine is 1:0.04 with the optimum proportioning of catalyst.
A kind of preparation side of the polymer of the conjugative monomer by the synthesis D-A type mental retardation gap length absorption of Suzuki coupling reaction
Method, has following steps:
(1) in reaction vessel, add 4 after bromination, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer
(Br-EDOTBT-Br), fluorenes or benzene or biphenyl or the diborate of triphenylamine, catalyst, part, weak base, then add in container
Solvent, by inflated with nitrogen after reaction vessel evacuation, is heated under 95 DEG C, stirring reacting 12-48h；Adding phenylboric acid, to react 2 little
Time, finally add bromobenzene and react 2 hours；
(2) reaction terminate after, products therefrom is sequentially added into methanol extraction, be recovered by filtration precipitation, dichloromethane dissolve sink
Shallow lake thing, cross post (wherein solid phase is silica gel, and flowing is mutually for dichloromethane), Rotary Evaporators evaporation and concentration, add methanol extraction,
Precipitation, vacuum drying treatment are recovered by filtration, finally give solid product and be target product；
Wherein, the diborate of fluorenes or benzene or biphenyl or triphenylamine particularly as follows: 2,7-double (4,4,5,5-tetramethyl-1,3,
2-dioxaborinate-diyl)-9,9-bis-fluorenes, Isosorbide-5-Nitrae-bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate-diyl)-benzene,
4,4 '-bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate-diyls)-1,1 '-biphenyl and 4,4 '-bis-(4,4,5,5-tetramethyls
Base-1,3,2-dioxaborinate-diyl) triphenylamine, its structural formula as shown in VI, VII, VIII, Ⅸ, R1, R2For H or (CH2)zCH3,
Wherein z number is 1-11,
Further, in described step (1), 4 after bromination, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer
(Br-EDOTBT-Br), the rate of charge of the diborate of fluorenes or benzene or biphenyl or triphenylamine is 1:1；
Catalyst is palladium catalyst, 4 after bromination, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-
EDOTBT-Br) it is 1:0.003-0.1 with fluorenes or the diborate total amount of benzene or biphenyl with the mol ratio of catalyst；
Part is in tricyclohexyl phosphine borofluoride, tricyclohexyl phosphine, tri-butyl phosphine, triphenylphosphine or triethylene diamine
One, the mol ratio of part and catalyst is 4-12:1；
Weak base be mass fraction be the tetramethylammonium hydroxide aqueous solution of 5-50%, mass fraction be four fourths of 5-50%
Base ammonium hydroxide aqueous solution, mass fraction be the tetraethyl ammonium hydroxide aqueous solution of 5-50%, mass fraction be the four of 5-50%
Propyl group ammonium hydroxide aqueous solution, mass fraction be the four hexyl ammonium hydroxide aqueous solutions of 5-50%, mass fraction be 5-50%'s
After one in four octyl group ammonium hydroxide aqueous solutions, potassium acetate or potassium carbonate, weak base and bromination 4,7-bis-(3,4-enedioxies
Thiophene)-diazosulfide monomer (Br-EDOTBT-Br) and fluorenes or benzene or biphenyl or triphenylamine diborate total amount mole
Ratio is 4-12:1；
Solvent is the one in benzene, toluene or dimethylbenzene, and its consumption is 4 after bromination, 7-bis-(3,4-enedioxy thiophenes
Fen)-diazosulfide monomer (Br-EDOTBT-Br) and the diborate total amount of fluorenes or benzene or biphenyl or triphenylamine mole dense
Degree is at 0.1-0.5mol/L；
After the consumption of phenylboric acid and bromination 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-
EDOTBT-Br) mol ratio is 1:1；The consumption of bromobenzene and fluorenes or the mol ratio of the diborate of benzene or biphenyl or triphenylamine
For 1:1.
Further preferably, described catalyst is Pd (OAC)2, PdCl2Or Pd (PPh (dppf)3)4In one, after bromination
4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfides monomer (Br-EDOTBT-Br) and fluorenes or benzene or the diborate of biphenyl
Total amount is 1:0.04 with the optimum proportioning of catalyst.
The polymer of the conjugative monomer mental retardation gap length using technical scheme gained absorbed is applied to preparation
Organic solar batteries, battery structure is: anode ITO/ hole transmission layer/active layer/(electron transfer layer)/negative electrode Al；Specifically
Preparation method is as follows:
(1) substrate of glass containing ITO being cleaned up, at ITO spin coating PEDOT/PSS solution, spin coating dries after annealing
Obtain hole transmission layer；
(2) by the low band gap conjugated polymer of gained of the present invention and butyl titanate (TBTT) or [6,6]-phenyl C61Butanoic acid
Methyl ester (PCBM) blend is dissolved in chloroform solvent and being spin-coated on hole transmission layer, and spin coating dries after annealing and obtains active layer；Altogether
Conjugated polymer and TBTT or PCBM mass ratio are 1:1-20；
(3) by the structure that obtains at vacuum condition (1 × 10-4Pa) the thick Al of one layer of 100nm it is deposited with under.
Spin coating described in step (1) and step (2) is divided into two steps, first step rotating speed to be 750r/min, and the time is 10s,
Second step rotating speed is 3000-4500r/min, and the time is 25-30s, and spin coating environment is air or nitrogen；Annealing temperature is 130-
200 DEG C, annealing time is 10-30min, and anneal environment is air.
Beneficial effect: the present invention is with 3, and 4-ethylenedioxythiophene (EDOT) is supplied for electronic unit, 2,1,3 diazosulfides
(BT) it is by electronic unit, uses Heck coupling reaction to be prepared novel D-A type conjugative monomer 4 by EDOT Yu BT, 7-bis-(3,
4-ethylenedioxy thiophene)-2,1,3-diazosulfide (EDOTBT), this D-A type conjugative monomer has stronger electronics push-and-pull effect
Should, high molecular can be prepared by Heck coupling reaction or Suzuki coupling reaction by above-mentioned D-A type conjugative monomer novel poly-
Compound, these polymer have low band gaps, wide absorption, higher phototranstormation efficiency and the feature of good film property, can be used as
The active layer of polymer solar battery, can be effectively improved the energy conversion efficiency (PCE) of polymer solar battery, suitably exist
Popularization and application in polymer solar battery.
Accompanying drawing explanation
The present invention is further described with embodiment below in conjunction with the accompanying drawings；
Fig. 1 is conjugative monomer 4 in embodiments of the invention 1,7-bis-(3,4-ethylene dioxythiophene)-2,1,3-benzo thiophene two
Azoles H-EDOTBT-H's1HNMR；
Fig. 2 is D-A type conjugative monomer 4 in embodiments of the invention 2,7-bis-(3,4-ethylene dioxythiophene)-2,1,3-benzene
And Br-EDOTBT-Br after thiadiazoles bromination1HNMR；
Fig. 3 is polymer P F6EDOTBT in embodiments of the invention 31HNMR；
Fig. 4 is the uv absorption figure of polymer P F6EDOTBT in embodiments of the invention 3；
Fig. 5 is the uv absorption figure of polymer P F8EDOTBT in embodiments of the invention 4.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited to the present embodiment.Implement
Example one
The synthesis of 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide conjugative monomer H-EDOTBT-H:
Reactions steps:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding the 4,7-of 0.147g (0.5mmol)
Two bromo-2,1,3-diazosulfides, 3,4 ethylenedioxy thiophenes of 0.142g (1mmol), the Pd of 0.0118g (0.0525mmol)
(OAC)2, tetrabutyl ammonium bromide TBAB of 0.498g (1.5mmol), the potassium carbonate K of 0.3628g (2.625mmol)2CO3, 8ml
DMF DMF.It is mixed uniformly, under nitrogen atmosphere 95 DEG C of reaction 12h stopped reaction.After reaction terminates,
Being poured into by products therefrom in distilled water and carry out extracting separatory with chloromethanes, wash three times, anhydrous magnesium sulfate is dried, and crosses post (wherein
Solid phase is alkali alumina, and flowing is toluene mutually: dichloromethane=1:1), with methanol extraction for several times, vacuum drying treatment, finally
Obtain solid product and be target product.Being vacuum dried 24h under the conditions of 80 DEG C, productivity is 40%, to product 4,7-bis-(3,4-
Ethylenedioxy thiophene)-diazosulfide conjugative monomer H-EDOTBT-H1HNMR is shown in Fig. 1.
Embodiment two
The synthesis of D-A type conjugative monomer Br-EDOTBT-Br:
Reactions steps:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding the 4,7-of 0.208g (0.5mmol)
The N-bromosuccinimide of two (3,4-ethylene dioxythiophene)-diazosulfides H-EDOTBT-H, 0.1780g (1mmol),
The acetic acid of 0.27g (4.5mmol), the chloroform of 12ml.The lower reaction of lucifuge ice bath stirring more than 24 hours, after reaction terminates, methanol
Precipitation, is recovered by filtration precipitation, vacuum drying treatment, finally gives solid product and be target product.Vacuum under the conditions of 100 DEG C
Being dried 24h, productivity is 80%.Fig. 2 is D-A type conjugative monomer Br-EDOTBT-Br synthesized in the present embodiment1HNMR。
Embodiment three
The copolymer p F6EDOTBT of D-A type conjugative monomer H-EDOTBT-H and 9,9-dihexyl fluorenes:
Polymerization procedure:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding the D-A of 0.2496g (0.6mmol)
Type conjugative monomer H-EDOTBT-H, 0.2952g (0.6mmol) 2,7-dibromo 9,9-dihexyl fluorenes, 0.0008g (0.0036mmol)
Pd (OAC)2, 0.0048g (0.0144mmol) tetrabutyl ammonium bromide TBAB, the potassium carbonate K of 0.6634g (4.8mmol)2CO3With
12mlN, the mixed solvent of dinethylformamide DMF.It is mixed uniformly, stops after 90 DEG C of reaction 12h under nitrogen atmosphere
Reaction.Reaction terminate rear methanol extraction, be recovered by filtration precipitation, again with dichloromethane dissolve after cross post (wherein solid phase is silica gel, flow
Dynamic mutually for dichloromethane), Rotary Evaporators concentrates, adds methanol extraction, precipitation, vacuum drying treatment is recovered by filtration, finally
Obtain solid product and be target product.Under the conditions of 80 DEG C, vacuum drying oven is dried 24h, and productivity is 54.2%.Fig. 3 is this enforcement
Polymer P F6EDOTBT's synthesized in example1HNMR, Fig. 4 are the uv absorption figures of polymer P F6EDOTBT.
Embodiment four
D-A type conjugative monomer Br-EDOTBT-Br and 9, the copolymer p F8EDOTBT of 9-dioctyl fluorene:
Polymerization procedure:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding 0.3444g (0.6mmol) D-A type
Conjugative monomer Br-EDOTBT-Br, 0.38556g (0.6mmol), 2,7-double (4,4,5,5-tetramethyl-1,3,2-dioxa boron
Alkane-diyl)-9,9-dioctyl fluorene, the Pd (OA of 0.004g (0.018mmol)C)2, 0.022g (0.20mmol) triethylene diamine
DABCO, 8ml mass fraction is the mixed solvent of 25%Et4NOH and 10ml toluene, is mixed uniformly, under nitrogen atmosphere 90
DEG C reaction 12h after stopped reaction.Add 0.0612g (0.5mmol) phenylboric acid reaction 2h, finally add 0.078g
(0.5mmol) bromobenzene reaction 2h.Methanol extraction, be recovered by filtration precipitation, again with dichloromethane dissolve after cross post (wherein solid phase is
Silica gel, flowing is mutually for dichloromethane), Rotary Evaporators concentrates, adds methanol extraction, is recovered by filtration at precipitation, vacuum drying
Reason, finally gives solid product and is target product.Under the conditions of 80 DEG C, vacuum drying oven is dried 24h, and productivity is 58.4%, Fig. 5
It it is the uv absorption figure of target product PF8EDOTBT.
Table 1 is embodiment three and the optical property data of embodiment four gained copolymer
Embodiment five
D-A type conjugative monomer H-EDOTBT-H and the copolymer of biphenyl:
Polymerization procedure:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding 0.2496g (0.6mmol) D-A type
Conjugative monomer H-EDOTBT-H, 0.1872g (0.6mmol), 4,4 '-two bromo-1,1 '-biphenyl, 0.0094g (0.042mmol)
Pd(OAC)2, 0.0619g (0.168mmol) tricyclohexyl phosphine borofluoride, 8ml mass fraction be 25% TPAOH
Aqueous solution and 10mlN, the mixed solvent of N-dimethyl acetylamide DMA.It is mixed uniformly, 90 DEG C of reactions under nitrogen atmosphere
Stopped reaction after 12h.Reaction terminates rear methanol extraction, precipitation is recovered by filtration, again by mistake post (wherein solid phase after dichloromethane dissolving
For silica gel, flowing is mutually for dichloromethane), Rotary Evaporators concentrates, adds methanol extraction, precipitation is recovered by filtration, is vacuum dried
Processing, finally give solid product and be target product, under the conditions of 80 DEG C, vacuum drying oven is dried 24h, and productivity is 53.4%.
Embodiment six
D-A type conjugative monomer Br-EDOTBT-Br and the copolymer of benzene:
Polymerization procedure:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding 0.3444g (0.6mmol) D-A type
Conjugative monomer Br-EDOTBT-Br, 0.198g (0.6mmol), Isosorbide-5-Nitrae-bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate-
Diyl)-benzene, the Pd (PPh of 0.028g (0.018mmol)3)4, 0.022g (0.20mmol) triethylene diamine DABCO, 8ml mass
Mark is 25%Et4The mixed solvent of NOH and 10ml toluene.It is mixed uniformly, stops after 90 DEG C of reaction 12h under nitrogen atmosphere
Only reaction.Add 0.0612g (0.5mmol) phenylboric acid reaction 2h, finally add the reaction of 0.078g (0.5mmol) bromobenzene
2h.Methanol extraction, be recovered by filtration precipitation, again with dichloromethane dissolve after cross post (wherein solid phase is silica gel, flowing be dichloromethane mutually
Alkane), Rotary Evaporators concentrate, add methanol extraction, precipitation, vacuum drying treatment are recovered by filtration, finally give solid product
It is target product.Under the conditions of 80 DEG C, vacuum drying oven is dried 24h, and productivity is 56.8%.
Embodiment seven
D-A type conjugative monomer Br-EDOTBT-Br and the copolymer of triphenylamine:
Polymerization procedure:
Equipped with thermometer, in the there-necked flask of the 100ml of stirrer, it is quantitatively adding 0.3444g (0.6mmol) D-A type
Br-EDOTBT-Br, 0.2982g (0.6mmol), 4,4 '-bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate-diyls) three
Aniline, the Pd (OA of 0.0269g (0.12mmol)C)2, 0.1615g (1.44mmol) triethylene diamine DABCO, 12ml mass divides
Number is 25% Tetramethylammonium hydroxide TMAOH and the mixed solvent of 30ml toluene.It is mixed uniformly, 90 DEG C under nitrogen atmosphere
Stopped reaction after reaction 12h.Add 0.0612g (0.5mmol) phenylboric acid reaction 2h, finally add 0.078g (0.5mmol)
Bromobenzene reaction 2h.Methanol extraction, be recovered by filtration precipitation, again with dichloromethane dissolve after cross post (wherein solid phase is silica gel, flowing
Mutually for dichloromethane), Rotary Evaporators concentrate, add methanol extraction, precipitation, vacuum drying treatment be recovered by filtration, final must
It is target product to solid product.Under the conditions of 80 DEG C, vacuum drying oven is dried 24h, and productivity is 56.8%.
Embodiment eight
The organic solar batteries that structure is ITO/PSS/PEDOT/PF6EDOTBT:PCBM/Al of preparation, step is as follows:
(1) being paved with by PSS/PEDOT on the ITO surface cleaned up, dried by spin coating, spin coating is divided into two steps: first
Step is 750 revs/min at rotating speed, spin coating 10s；Second step is 3400 revs/min at rotating speed, spin coating 30s, at 120 DEG C after terminating
Anneal in air 30min, and thickness is: 100nm.I.e. obtain organic solar batteries hole transmission layer；
(2) the copolymer p F6EDOTBT obtained by above-described embodiment adds PCBM and stirs use after joining in chloroform
0.45um filter filters (PF6EDOTBT Yu PCBM mass ratio: 1:1), spin coating (the first rotating speed 750r/min, 10s；Second
Turn 3900r/min, 30s) on the hole transmission layer prepared, spin coating terminates rear 120 DEG C of 10min that anneal in atmosphere.Thickness
For 100nm, i.e. obtain the active layer of battery；
(3) by the structure that obtains at vacuum condition (1 × 10-4Pa) the thick Al of one layer of 100nm it is deposited with under.Gained solar-electricity
The photovoltaic performance parameter testing in pond the results are shown in Table 2.
The photovoltaic test result of table 2 solaode
。
Claims (6)
1. the preparation method of the D-A type conjugative monomer of a mental retardation gap length absorption, it is characterised in that: the structural formula of described monomer
For:
Wherein, R is H or Cl, and the preparation method of this monomer has following steps:
(1) add in reaction vessel 3,4-ethylene dioxythiophene, 4, bromo-2,1,3-diazosulfide, the catalyst of 7-bis-, join
Body, weak base, then in container, add solvent, by inflated with nitrogen after reactor evacuation, it is heated under 90 DEG C, stirring reacting 12-
48h；
(2), after reaction terminates, products therefrom is poured in distilled water and carry out extracting separatory with dichloromethane, wash three times, anhydrous
Magnesium sulfate is dried, and crosses post, by methanol extraction 3-5 time, vacuum drying treatment, obtains solid product and is target product 4,7-bis-
(3,4-ethylene dioxythiophene)-diazosulfide；
(3) by the target product 4 of above-mentioned gained, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide adds N-halo amber
Amber acid imide, glacial acetic acid, then in container, add solvent, under lucifuge ice bath stirring condition, react 24-48h；
(4), after reaction terminates, dissolve with 1-Methyl-2-Pyrrolidone after rotary evaporation is dry, methanol extraction, precipitation be recovered by filtration,
Vacuum drying treatment, obtains solid product and is target product.
The preparation method of the D-A type conjugative monomer that mental retardation gap length the most according to claim 1 absorbs, it is characterised in that: institute
Stating in step (1), 3,4-ethylene dioxythiophene and 4, the rate of charge of bromo-2,1, the 3-diazosulfide of 7-bis-is (2+x1): 1, x1For
0.1-0.5；
Catalyst is palladium catalyst, 3,4-ethylene dioxythiophene and 4, bromo-2,1,3-diazosulfide total amount and the catalyst of 7-bis-
Mol ratio be 1:0.003-0.1；
Part is tetrabutyl ammonium bromide, tricyclohexyl phosphine borofluoride, tricyclohexyl phosphine, three dredges butyl phosphine, triphenylphosphine or three
One in ethylene diamine, part is 4-12:1 with the mol ratio of catalyst；
Weak base be potassium carbonate, potassium acetate, mass fraction be the tetramethylammonium hydroxide aqueous solution of 5-50%, mass fraction be 5-
The TBAH aqueous solution of 50%, mass fraction are that the tetraethyl ammonium hydroxide aqueous solution of 5-50%, mass fraction are
The TPAOH aqueous solution of 5-50%, mass fraction are four hexyl ammonium hydroxide aqueous solution or the mass fractions of 5-50%
For the one in the four octyl group ammonium hydroxide aqueous solutions of 5-50%, alkali is 30-80:1 with the mol ratio of catalyst；
Solvent is DMF or N,N-dimethylacetamide, and its consumption is 3,4-ethylene dioxythiophene and 4,7-bis-
The molar concentration of bromo-2,1,3-diazosulfide total amount is at 0.1-0.5mol/L；
In described step (3), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfides feed intake with N-halosuccinimides
Ratio is 1:(2+x2), x2For 0.1-5；
Glacial acetic acid and 4, the mol ratio of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide is 9:1；
Solvent is chloroform or oxolane, and its consumption is 4,7-bis-(3,4-ethylene dioxythiophene)-2,1,3-diazosulfide and
The molar concentration of N-halosuccinimides total amount is at 0.1-5mol/L.
The preparation method of the D-A type conjugative monomer that mental retardation gap length the most according to claim 2 absorbs, it is characterised in that: institute
Stating catalyst is Pd (OAC)2、PdCl2Or Pd (PPh (dppf)3)4In one, 3,4-ethylene dioxythiophene and 4,7-bis-bromo-2,
1,3-diazosulfide total amount is 1:0.035 with the mol ratio of catalyst.
4. a preparation method for the polymer of the D-A type conjugative monomer absorbed containing the mental retardation gap length described in claim 1, its
It is characterised by: the structural formula of this polymer is:
The number-average molecular weight of polymer is 1000-
100000；
Wherein, n is 1-10；X is 0.05-0.95；R3For H or Br；
Ar isOrIn one, R2For H or (CH2)zCH3, wherein z number is 1-11；Described
The preparation method of polymer of the D-A type conjugative monomer absorbed containing mental retardation gap length there are following steps:
(1) addition 4 in reaction vessel, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer, Isosorbide-5-Nitrae-dibromobenzene or 4,
4 '-two bromo-1,1 '-biphenyl or 4, the one in 4 '-dibromo triphenylamine, catalyst, part, weak base, then add molten in container
Agent, by inflated with nitrogen after reaction vessel evacuation, is heated to 95 DEG C, reacts 12-48h under stirring condition；
(2) reaction terminate after, products therefrom is sequentially added into methanol extraction, be recovered by filtration precipitation, dichloromethane dissolution precipitation thing,
Cross post, Rotary Evaporators evaporation and concentration, add methanol extraction, precipitation, vacuum drying treatment are recovered by filtration, finally give solid
Product is target product.
The preparation method of the polymer of the D-A type conjugative monomer containing the absorption of mental retardation gap length the most according to claim 4, its
Be characterised by: in described step (1), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomers and 2,7-dibromo fluorenes or
Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, a kind of molar feed ratio in 4 '-dibromo triphenylamine is 0.5-1:
1；
Catalyst is palladium catalyst, 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomers and 2,7-dibromo fluorenes or 1,
4-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, a kind of total amount in 4 '-dibromo triphenylamine and the mol ratio of catalyst
For 1:0.003-0.1；
Part is tetrabutyl ammonium bromide, tricyclohexyl phosphine borofluoride, tricyclohexyl phosphine, three dredges butyl phosphine, triphenylphosphine or three
One in ethylene diamine, part is 4-12:1 with the mol ratio of catalyst；
Weak base be potassium carbonate, potassium acetate, mass fraction be the tetramethylammonium hydroxide aqueous solution of 5-50%, mass fraction be 5-
The TBAH aqueous solution of 50%, mass fraction are that the tetraethyl ammonium hydroxide aqueous solution of 5-50%, mass fraction are
The TPAOH aqueous solution of 5-50%, mass fraction are four hexyl ammonium hydroxide aqueous solution or the mass fractions of 5-50%
For the one in the four octyl group ammonium hydroxide aqueous solutions of 5-50%, alkali and 4,7-bis-(3,4-ethylene dioxythiophene)-benzo thiophene two
Azoles monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4, the one in 4 '-dibromo triphenylamine
The mol ratio of total amount be 4-12:1；
Solvent is DMF, N,N-dimethylacetamide, and its consumption is 4,7-bis-(3,4-ethylene dioxythiophene)-
Diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4,4 '-dibromo triphenylamine
In the molar concentration of a kind of total amount at 0.1-0.5mol/L.
The preparation method of the polymer of the D-A type conjugative monomer containing the absorption of mental retardation gap length the most according to claim 5, its
It is characterised by: described catalyst is Pd (OAC)2、PdCl2Or Pd (PPh (dppf)3)4In one, 4,7-bis-(3,4-ethylenes two
Oxygen thiophene)-diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-two bromo-1,1 '-biphenyl or 4,4 '-two
A kind of total amount in bromine triphenylamine is 1:0.04 with the proportioning of catalyst.
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