CN105399930B - One kind is used for organic semi-conductor conjugated polymer and preparation method thereof - Google Patents
One kind is used for organic semi-conductor conjugated polymer and preparation method thereof Download PDFInfo
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- CN105399930B CN105399930B CN201510989075.1A CN201510989075A CN105399930B CN 105399930 B CN105399930 B CN 105399930B CN 201510989075 A CN201510989075 A CN 201510989075A CN 105399930 B CN105399930 B CN 105399930B
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004065 semiconductor Substances 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 8
- 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 8
- 239000003446 ligand Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006619 Stille reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 230000005669 field effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 8
- 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 8
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 125000005605 benzo group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 4
- 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 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 description 4
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- 239000007791 liquid phase Substances 0.000 description 4
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- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 230000004044 response Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 0 *=*C(NCN1)=C1P Chemical compound *=*C(NCN1)=C1P 0.000 description 2
- SYBUMOIKKHDLBN-UHFFFAOYSA-N C(=C)S(=O)(=O)O.C1=CC=CC=C1 Chemical compound C(=C)S(=O)(=O)O.C1=CC=CC=C1 SYBUMOIKKHDLBN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- -1 benzo selenium Diazole Chemical compound 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 239000007795 chemical reaction product Substances 0.000 description 2
- 210000001072 colon Anatomy 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- RAUWPNXIALNKQM-UHFFFAOYSA-N 4-nitro-1,2-phenylenediamine Chemical class NC1=CC=C([N+]([O-])=O)C=C1N RAUWPNXIALNKQM-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- SIUXRPJYVQQBAF-UHFFFAOYSA-N O=C(c1c2[s]cc1)c([s]cc1)c1C2=O Chemical compound O=C(c1c2[s]cc1)c([s]cc1)c1C2=O SIUXRPJYVQQBAF-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTUIEFKAUSEAIM-UHFFFAOYSA-N c1c[s]c(/C(/c2c3[s]cc2)=C2/SC=CS2)c1/C3=C1\SC=CS1 Chemical compound c1c[s]c(/C(/c2c3[s]cc2)=C2/SC=CS2)c1/C3=C1\SC=CS1 VTUIEFKAUSEAIM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- 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
-
- 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
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Abstract
It is used for organic semi-conductor conjugated polymer and preparation method thereof the invention discloses one kind, the general structure of conjugated polymer is as follows：Wherein, n is the natural number between 10~100；R1For H or C1~C20Alkyl, R2For C1~C10Alkyl.The conjugated polymer can be used in organic solar batteries device, organic electroluminescence device, organic field effect tube, organic laser etc..
Description
Technical field
The present invention relates to conjugated polymer and its preparation of organic semiconductor material field, more particularly to a kind of photoelectric functional
Method and application.
Background technology
Organic solar batteries are such as with low cost due to some incomparable advantages of inorganic solar cell, system
Make technique simple, product weight is light, can large area flexible the advantages of prepare, as one kind have potential regenerative resource by
The extensive concern of people.In past ten years, the performance of organic solar batteries, which has, to be steadily improved, and energy conversion efficiency is
Close to 10%.
Although people have put into numerous studies in terms of organic solar batteries, and achieve development at full speed, You Jitai
The efficiency of positive energy battery has obtained large increase, but the energy conversion efficiency of organic solar batteries still compares silicon solar at present
Battery is low, and one of reason is carrier mobility several orders of magnitude lower than the mobility of inorganic monocrystalline material of polymer.
The spectral response of conjugated polymer photocell material is relatively carried used at present, and its absorption spectrum can not be well with solar spectrum
Matching, is another major reason for causing energy transfer efficiency low
Therefore, the light abstraction width of polymeric material how is widened, its light abstraction width is farthest covered entirely
Sunshine spectrum by be research emphasis.
The content of the invention
It is used for organic semi-conductor conjugated polymer and its preparation method and application it is an object of the invention to one kind.
Technical scheme is as follows：
One kind is used for organic semi-conductor conjugated polymer, and general structure is as follows：
Wherein, n is the natural number between 10~100；R1For H or C1~C20Alkyl, R2For C1~C10Alkyl.
The above-mentioned preparation method for organic semi-conductor conjugated polymer, comprises the following steps：
Compound I and compound II with following structural formula are provided respectively：
Wherein, R1For H or C1~C20Alkyl, R2For C1~C10Alkyl；
Under protective gas atmosphere, anhydrous and oxygen-free environment, by the compound I and compound II in organic solvent and
Catalyst carries out Stille coupling reactions under conditions of existing, wherein, the compound I and the compound II mol ratio are
1:1.5~1.5:1, reaction temperature is 80 DEG C~100 DEG C, and the reaction time is 48h~72h, is obtained after isolating and purifying with as follows
The conjugated polymer of structural formula：
Wherein, n is the natural number between 10~100.
The addition of the catalyst is the 0.01%~5% of the molal quantity of the compound II；The catalyst is to have
The mixture of machine palladium and organophosphorus ligand.
In the mixture of the organic palladium and organophosphorus ligand, the mol ratio of the organic palladium and the organophosphorus ligand is
1:5~1:10；The organic palladium is three (dibenzalacetone) two palladium；The organophosphorus ligand is three (o-methyl-phenyl) phosphines.
The organic solvent is tetrahydrofuran, N,N-dimethylformamide or toluene.
The compound I is made by following steps：
Compound C and compound D with following structural formula are provided：
Under conditions of protective gas atmosphere, -78 DEG C, lithium diisopropyl amido is added into the organic molten of the compound C
In liquid, wherein, the lithium diisopropyl amido and the compound C mol ratio are 1:1~1.5:1, stirring reaction 2h~3h,
Then compound D is added into above-mentioned system and carries out Wittig-Horner reactions, wherein, the compound D and the compound
C mol ratio is 1:2.0~1:Recover to room temperature to continue to react 12h~15h after 2.5 reaction 0.5h~1h, after isolating and purifying
To the compound E with following structural formula：
Under conditions of protective gas atmosphere, -78 DEG C, in the organic solution that n-BuLi is added to the compound E, its
In, the n-BuLi and the compound E mol ratio are 2.2:1~2.5:1, stirring reaction 2h~3h, then to above-mentioned
Trimethyltin chloride is added in system, wherein, the trimethyltin chloride and the compound E mol ratio are 2.0:1~
2.5:Recover to room temperature to continue to react 20h~24h after 1, reaction 0.5h~1h, obtain the compound I with following structural formula：
The compound II is made by following steps：
Compound F and compound G is provided, the structural formula of the compound F is：
The structural formula of the compound G is：
Wherein, R2For C1~C10Alkyl；And
In inert gas shielding atmosphere, the compound F and compound G are dissolved in the first solvent and obtain the first mixing
Liquid, catalyst and alkali are instilled into first mixed liquor, in stirring reaction 4 hours at 130 DEG C, obtain described after isolating and purifying
Compound II；Wherein, the mole of the catalyst is the 10% of the mole of the compound F, the alkali and the chemical combination
Thing G mol ratio is 1: 1；The mol ratio of the compound F and compound G are 1:2.
The compound F is made by following methods：
It is 22.95g by solid-to-liquid ratio:2mL:2- amino -5- nitroanilines and pyridine are dissolved in thionyl chloride by 100mL, in
80 DEG C~90 DEG C back flow reactions 24 hours, stop after reaction, reaction solution are heated into 80 DEG C and rotates out excessive thionyl chloride
(SOCl2), reaction product is cooled to room temperature, is poured into a large amount of water, is dried in vacuo after stirring, filtering, washing, obtains pure
5- nitros -2,1,3 diazosulfides obtain 5- nitros -2,1,3 diazosulfides.
By 5- nitros -2,1,3 diazosulfides are carried out being mixed to get mixture with hydrobromic acid, and mixture is warming up into 127
DEG C backflow, was added dropwise bromine to mixture in 30 minutes and flows back 4 hours, reaction solution heat filtering is refiltered after filtrate cooling,
Filter residue substantial amounts of water washing and drying, then, obtain pure 4,7- with glacial acetic acid recrystallization once with Gossypol recrystallized from chloroform once
The two bromo- diazosulfides of 5- nitros -2,1,3.Wherein, 5- nitros -2,1, the solid-to-liquid ratio of 3 diazosulfides, hydrobromic acid and bromine
For 10.35g:15ml:11.3ml.
By the bromo- 5- nitros -2,1 of 4,7- bis-, 3 diazosulfides are added in DMF with copper powder, are heated to
120 DEG C are reacted 3 hours, and reaction solution is cooled into room temperature, add 90ml toluene, are stirred 30 minutes, filtering, filtrate saturated common salt
Water and water washing, merge organic layer, and anhydrous magnesium sulfate is dried, and filtering, revolving is dry, and absolute ethyl alcohol recrystallization obtains pure 4,
4 '-two bromo- 6,6 '-dinitros-diazosulfide of connection 2,1,3.Wherein, the bromo- 5- nitros -2,1 of 4,7- bis-, 3 diazosulfides, copper
The solid-to-liquid ratio of powder and N,N-dimethylformamide is 10.2g:9.5g:90mL.
By 4,4 '-two bromo- 6, the diazosulfide of 6 '-dinitro-connection 2,1,3 is added in tetrahydrofuran, then adds chlorination
Tin, is warming up to 100 DEG C, is heated to reflux 10 hours, and 4,4 '-two bromo- 6,6 '-two iodo- 2,1,3- benzo are obtained after isolating and purifying
Thiadiazoles.Wherein, 4,4 '-two bromo- 6, the solid-to-liquid ratio of the diazosulfide of 6 '-dinitro-connection 2,1,3, tetrahydrofuran and stannic chloride
For 10.3g:300mL:40g.
By 4,4 '-two bromo- 6,6 '-two iodo- 2,1,3- diazosulfide adds in ethanol and obtains suspension, by suspension
0 DEG C is cooled to, sodium borohydride is then added, reacts 20 hours at room temperature, 4,4 '-two bromo- 6,6 '-two is obtained after isolating and purifying
Iodo- di- (1,2- phenylenediamines).Wherein, 4,4 '-two bromo- 6,6 '-two iodo- 2,1,3- diazosulfide, ethanol and hydroboration
The solid-to-liquid ratio of sodium is：6.80g:200mL:14g.
4,4 '-two bromo- 6,6 '-two iodo- di-s (1,2- phenylenediamine) and ethanol are mixed to get the second mixture, by second
Mixture is flowed back, and the selenium dioxide aqueous solution is added dropwise, and backflow was filtered reaction solution after 2 hours, obtained compound II.
Wherein, the solid-to-liquid ratio of 4,4 '-two bromo- 6,6 '-two iodo- di-s (1,2- phenylenediamine), ethanol and selenium dioxide is：
3.12g:60mL:1.17g；In the selenium dioxide aqueous solution, the concentration of selenium dioxide is 53.2mg/mL.
Described is used for organic semi-conductor conjugated polymer in organic solar batteries device, organic electroluminescence
Application in part, organic field effect tube or organic laser.
The beneficial effects of the invention are as follows：
In above-mentioned conjugated polymer, benzo [1,2-b:4,5-b '] Dithiophene has good symmetry and flatness, tool
There is good carrier mobility, be a kind of excellent electron donor material；The radius ratio benzo of selenium atom in selenole
Sulphur atom in thiadiazoles is big, and the molecule that can more strengthen between polymer chain is overlapping, promotes the hopping process of electric charge, with knot
Structure is simple, symmetrical, the advantages of electron delocalization performance is good, and is planar conjugate structure, and carrier mobility is high.Thus, benzo selenium
Diazole has more preferable electronic transport property than diazosulfide, and with the energy gap and wider light of outstanding regulation material
Spectrum response, is a kind of very excellent acceptor material.Therefore, conjugated polymer of the invention can be formed it is a kind of it is very strong to
Body-receptor structure, is on the one hand conducive to improving the charge transport quality and stability of material, on the other hand advantageously reduces material
The band gap of material, so as to expand sun light abstraction width, improves electricity conversion, with carrier mobility is higher, spectrum
The wider advantage of response.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
Present embodiment discloses the following conjugated polymer P1 of structural formula：
Wherein, n=30, R1For C16H33, R2For C10H21。
Conjugated polymer P1 preparation process is as follows：
First, the preparation of the compound A with following structural formula：
Compound A preparation method comprises the following steps：
1st, under nitrogen protection, by (cetyl) -1,3- of 1.32g (2.0mmol) 2- dimethoxys phosphono -4,5- bis-
The 60mL anhydrous tetrahydrofuran solutions of two mercaptan (C) are cooled to -78 DEG C, are slowly added to the LDA that 2.0mL concentration is 1.5M
The cyclohexane solution of (3.0mmol), is finished, at -78 DEG C after stirring reaction 3h, add 0.22g (1.0mmol) benzo [1,
2-b:4,5-b '] the 10mL anhydrous tetrahydrofuran solutions of Dithiophene -4,8- diketone (D) carry out Wittig-Horner reactions, insulation
Room temperature is returned to after reaction 0.5h, continues to react 12h, stops reaction.Rotary evaporation removes excessive tetrahydrofuran, and what is obtained is thick
Product produces product 4,8- bis- (mercaptan -2- aldehyde of 4,5- bis- (cetyl) -1,3- bis-) benzo through silica gel column chromatography separating purification
[1,2-b:4,5-b '] Dithiophene (E).The eluant, eluent of column chromatography for separation is that volume ratio is 4:1 n-hexane and dichloromethane it is mixed
Compound, yield is 47%, MS (EI) m/z:1290(M+).Reaction equation is as follows：
2nd, under nitrogen protection, by (mercaptan-the 2- of 4,5- bis- (cetyl) -1,3- bis- of 2.58g (2.0mmol) 4,8- bis-
Aldehyde) benzo [1,2-b:4,5-b '] the 60mL anhydrous tetrahydrofuran solutions of Dithiophene (E) are cooled to -78 DEG C, are slowly added to 2.0mL
Concentration is 2.5M n-BuLi (5.0mmol) hexane solution, finishes, at -78 DEG C after stirring reaction 2h, adds
Room temperature is returned to after 1.5mL (5.0mmol) trimethyltin chloride, insulation reaction 0.5h, continues to react 24h, obtains product, i.e.,
2,6- bis- (tin trimethyl) -4,8- two (mercaptan -2- aldehyde of 4,5- bis- (cetyl) -1,3- two) benzo [1,2-b:4,5-b '] two
Thiophene (A), MS (EI) m/z:1616(M+).Its reaction equation is as follows：
2nd, the bromo- 6,7- bis- of prepare compound B -4,9- bis- (3,7- dimethyl) octyl group-benzo [2,1-e:3,4-e] two
(selenole)
(1) diazosulfide of prepare compound 5- nitros -2,1,3
2- amino -5- nitroanilines (22.95g, 0.15mol) and 100ml thionyl chlorides, stirring are added in three-necked flask
And 2ml pyridines are slowly added dropwise, heating stops reaction after 90 DEG C of back flow reaction 24h, be heated to 80 DEG C rotate out it is excessive
SOCl2Afterwards, reaction product is cooled to room temperature, be poured into a large amount of water, be dried in vacuo after stirring, filtering, washing, obtain product 5-
Nitro -2,1,3 diazosulfide 21.7g, yield 80%.
Reaction equation is as follows：
(2) the bromo- diazosulfides of 5- nitros -2,1,3 of prepare compound 4,7- bis-
5- nitros -2,1,3 diazosulfides (10.35g, 60mmol) and 40% hydrobromic acid are added in three-necked flask
15ml, is warming up in 127 DEG C of backflows, 30min and bromine 11.3ml is slowly added dropwise and the 4h that flows back, heat filtering, filtrate cooling after after
Filter, solid substantial amounts of water washing and drying, then, obtain product with glacial acetic acid recrystallization once with Gossypol recrystallized from chloroform once
10.2g, yield：50%.
Reaction equation is as follows：
(3) the bromo- 6,6 '-dinitro of prepare compound 4,4 '-two-diazosulfide of connection 2,1,3
Add in three-necked flask 4,7- bis- bromo- diazosulfides of 5- nitros -2,1,3 (10.2g, 30mmol), 9.5g
Copper powder and 90ml DMF (DMF), be heated to 120 DEG C reaction 3 hours after, stop reaction, be cooled to room temperature,
90ml toluene is added, is stirred 30 minutes, is filtered, filtrate saturated aqueous common salt and water washing merge organic layer, and anhydrous magnesium sulfate is done
Dry, filtering, revolving is dry, absolute ethyl alcohol recrystallization, obtains product 4,4 '-two bromo- 6, the diazosulfide of 6 '-dinitro-connection 2,1,3
4.7g, yield 30.2%.
Reaction equation is as follows：
(4) the iodo- 2,1,3- diazosulfides of prepare compound 4,4 '-two bromo- 6,6 '-two
In three-necked flask, addition 4,4 '-two bromo- 6, the diazosulfide of 6 '-dinitro-connection 2,1,3 (10.3g,
20mmol), the tetrahydrofuran THF that 300ml is dried is added, adds 40g SnCl2(200mmol), is warming up to 100 DEG C, heats back
10h is flowed, stops reaction, cooling adjusts pH value to 8.0, absolute ether extraction, revolving gained organic layer is obtained with sodium hydroxide solution
To solid crude product, it is put into three-necked flask, 58ml hydrochloric acid (21.7mmol) is added, in agitation and dropping nitrous acid in 30 minutes
Sodium solution 20ml (37.7mmol), temperature control is below 5 DEG C, and solution is in yellow, after completion of dropping, reacts 30 minutes.Then
Reacted solution is added dropwise in liquor kalii iodide (62g KI+100ml water), is stirred vigorously, 12h is reacted.Stop anti-
Should, adjust pH value to 7.0 with sodium hydroxide solution, extracted with absolute ether, organic layer washing, anhydrous magnesium sulfate is dried, and is filtered, rotation
Filtrate is evaporated, silica gel column chromatography post separation is used, recrystallizing methanol is then carried out, 4.1g4 is obtained, 4 '-two bromo- 6,6 '-two iodo- 2,
1,3 diazosulfide, yield is 30%.
Reaction equation is as follows：
(5) the iodo- di- (1,2- phenylenediamines) of prepare compound 4,4 '-two bromo- 6,6 '-two
In three-necked flask, addition 4,4 '-two bromo- 6,6 '-two iodo- 2,1,3 diazosulfide (6.80g,
0.01mol), 200ml ethanol is added, suspension is formed, 0 DEG C is added dropwise sodium borohydride (14g, 0.37mol), at room temperature mixture
Stirring reaction 20 hours, stops reaction, is extracted with absolute ether, and organic layer washing, anhydrous magnesium sulfate is dried, and filtering, revolving is dry
Filtrate, obtains 5.49g products, yield 88%.
Reaction equation is as follows：
(6) the iodo- 2,1,3- selenoles of prepare compound 4,4 '-two bromo- 6,6 '-two
In three-necked flask, 4,4 '-two bromo- 6,6 '-two iodo- di-s (1,2- phenylenediamine) (3.12g, 5mmol) are added, plus
Enter 60ml ethanol solution, flow back, SeO is added dropwise2(1.17g, 10.5mmol) aqueous solution (hot water 22ml), reactant mixture backflow
2 hours, stop reaction, filtering obtains 3.48g products, yield 90%.
Reaction equation is as follows：
(7) the bromo- 6,7- bis- of prepare compound B -4,9- bis- (3,7- dimethyl) octyl group-benzo [2,1-e:3,4-e] two
(selenole)
Add 4,4 '-two bromo- 6,6 '-two iodo- 2 in three-necked flask, 1,3 selenole (3.87g, 5mmol), 2,
6,13,17- tetramethyl -9- octadecynes (3.07g, 10mmol) and 25ml DMF, are passed through nitrogen gas stirring 20min, add Bu3N
(0.907g, 10mmol) and Pd (OAc)2(115mg, 0.5mmol), is warming up to 130 DEG C, heats 4h, cools down, washing, dichloromethane
Alkane is extracted, and obtains organic layer, and anhydrous sodium sulfate drying, filtering, vacuum distillation, silica gel column chromatography post separation obtains 2.48g products 4,
9- bis- bromo- 6,7- bis- (3,7- dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole), yield 60%.
3rd, conjugated polymer P1 synthesis
Under nitrogen protection, by 1.2mmol2,6- bis- (tin trimethyl) -4,8- bis- (4,5- bis- (cetyl) -1,3- bis-
Mercaptan -2- aldehyde) benzo [1,2-b:4,5-b '] Dithiophene A and 0.8mmol compounds B are added in the toluene of 80mL dryings, drum
Steep 0.5h and remove the oxygen of residual, then be rapidly added catalyst Pd2(dba)3(7.3mg, 0.008mmol) and P (o-Tol)3
(4.86mg, 0.016mmol), bubbling 1h removes the oxygen of residual, and back flow reaction 30h, mixed liquor is evaporated under reduced pressure at 120 DEG C
Excessive toluene is removed, then residual liquid is added drop-wise in methanol and settled, the solid obtained after suction filtration is washed with methanol,
Rear oxidation aluminium column chromatography is dried, then chloroform elutes and collects washing lotion, evaporation removes and collects remaining after the organic solvent in washing lotion
Liquid is added drop-wise in methanol and settled, the solid collected after suction filtration acetone surname extraction three days, collects liquid phase and by liquid phase
It is added drop-wise in methanol and is settled, night is pumped through under vavuum pump, obtained solid is conjugated polymer P1 after purification.
Embodiment 2
Present embodiment discloses the following conjugated polymer P2 of structural formula：
Wherein, n=10, R1For H, R2For C10H21。
Conjugated polymer P2 preparation process is as follows：
First, the preparation of the compound A with following structural formula：
Compound A preparation method comprises the following steps：
1st, under nitrogen protection, by the 40mL of the mercaptan (C) of 0.42g (2.0mmol) 2- dimethoxys phosphono -1,3- bis- without
Water tetrahydrofuran solution is cooled to -78 DEG C, is slowly added to the cyclohexane solution that 2.0mL concentration is 1.5M LDA (3.0mmol), plus
Finish, at -78 DEG C after stirring reaction 3h, add 0.22g (1.0mmol) benzo [1,2-b:4,5-b '] Dithiophene -4,8- two
The 10mL anhydrous tetrahydrofuran solutions of ketone (D) return to room temperature after carrying out Wittig-Horner reactions, insulation reaction 0.5h, after
Continuous reaction 12h, stops reaction.Rotary evaporation removes excessive tetrahydrofuran, and obtained crude on silica gel column chromatography for separation is pure
Change, produce product 4,8- bis- (1,3- bis- mercaptan -2- aldehyde) benzo [1,2-b:4,5-b '] Dithiophene (E).Column chromatography for separation is washed
De- agent is that volume ratio is 5:1 n-hexane and the mixture of dichloromethane, yield are 55%, MS (EI) m/z:393(M+).Reaction
Formula is as follows：
2nd, under nitrogen protection, by 0.79g (2.0mmol) 4,8- bis- (1,3- bis- mercaptan -2- aldehyde) benzo [1,2-b:4,5-
B '] the 40mL anhydrous tetrahydrofuran solutions of Dithiophene (E) are cooled to -78 DEG C, are slowly added to the n-BuLi that 2.0mL concentration is 2.5M
The hexane solution of (5.0mmol), is finished, at -78 DEG C after stirring reaction 2h, adds 1.5mL (5.0mmol) trimethyl
Room temperature is returned to after stannic chloride, insulation reaction 0.5h, continues to react 24h, obtains product, i.e. 2,6- bis- (tin trimethyl) -4,8-
Two (mercaptan -2- aldehyde of 1,3- bis-) benzo [1,2-b:4,5-b '] Dithiophene (A), MS (EI) m/z:718(M+).Reaction equation is as follows：
2nd, the bromo- 6,7- bis- of prepare compound B -4,9- bis- (3,7- dimethyl) octyl group-benzo [2,1-e:3,4-e] two
(selenole)
With reference to the corresponding preparation process in embodiment 1.
3rd, conjugated polymer P2 synthesis
Under nitrogen protection, by 2.0mmol 2,6- bis- (tin trimethyl) -4,8- bis- (1,3- bis- mercaptan -2- aldehyde) benzo
[1,2-b:4,5-b '] Dithiophene (A) and 2.0mmol compounds B are added to 80mL and dried in DMF, and bubbling 0.5h removes residual
Oxygen, then it is rapidly added catalyst Pd2(dba)3(7.3mg, 0.008mmol) and P (o-Tol)3(48.6mg, 0.16mmol), drum
The oxygen that 1h removes residual is steeped, mixed liquor is evaporated under reduced pressure and removes excessive DMF by the back flow reaction 24h at 80 DEG C, then will be residual
Extraction raffinate body, which is added drop-wise in methanol, to be settled, and the solid obtained after suction filtration is washed with methanol, dries rear oxidation aluminium column chromatography, then
Chloroform is eluted and collects washing lotion, and evaporation, which removes to collect remaining liq after the organic solvent in washing lotion and be added drop-wise in methanol, is sunk
Drop, the solid collected after suction filtration acetone surname extraction three days collects liquid phase and liquid phase is added drop-wise in methanol and settled, very
Night is pumped through under empty pump, obtained solid is conjugated polymer P2 after purification.
Embodiment 3
A kind of organic solar batteries device, using glass as substrate, tin indium oxide (ITO) is used as conductive layer, conjugation
Polymer uses the conjugated polymer P1 in embodiment 1.
The structure of the organic solar batteries device is：Glass/ITO/PEDOT:PSS/ active layers/Al, wherein, ITO is
Square resistance is 10 Ω/~20 Ω/ tin indium oxide.PEDOT is poly- (3,4- Ethylenedioxy Thiophene), and PSS is poly- (benzene
Vinyl sulfonic acid).The material of active layer be mixture, including using conjugated polymer P1 as the electron donor material of material and with [6,
6] phenyl-C61- methyl butyrate ([6,6]-phenyl-C61-butyric acid methyl ester, PCBM) is the electricity of material
Sub- acceptor material.
The manufacturing process of the organic solar batteries device is as follows：
Ito glass is handled with oxygen-Plasma after ultrasonic wave is cleaned, PEDOT is coated on ITO:PSS layer, wherein,
Colon "：" represent mixing.
In PEDOT:In PSS layer, active layer is coated using spin coating technique, the material of active layer is mixture, including with altogether
Conjugated polymer P1 is for the electron donor material of material and with [6,6] phenyl-C61- methyl butyrate ([6,6]-phenyl-C61-
Butyric acid methyl ester, PCBM) be material electron acceptor material.
Metallic aluminum is prepared using vacuum evaporation technology on active layer, metallic aluminum obtains organic sun as negative electrode
Can battery device Q1.
Embodiment 4
A kind of organic solar batteries device, using glass as substrate, tin indium oxide (ITO) is used as conductive layer, conjugation
Polymer uses the conjugated polymer P2 in embodiment 2.
The structure of the organic solar batteries device is：Glass/ITO/PEDOT:PSS/ active layers/Al, wherein, ITO is
Square resistance is 10 Ω/~20 Ω/ tin indium oxide.PEDOT is poly- (3,4- Ethylenedioxy Thiophene), and PSS is poly- (benzene
Vinyl sulfonic acid).The material of active layer be mixture, including using conjugated polymer P2 as the electron donor material of material and with [6,
6] phenyl-C61- methyl butyrate ([6,6]-phenyl-C61-butyric acid methyl ester, PCBM) is the electricity of material
Sub- acceptor material.
The manufacturing process of the organic solar batteries device is as follows：
Ito glass is handled with oxygen-Plasma after ultrasonic wave is cleaned, PEDOT is coated on ITO:PSS layer, wherein,
Colon "：" represent mixing.
In PEDOT:In PSS layer, active layer is coated using spin coating technique, the material of active layer is mixture, including with altogether
Conjugated polymer P1 is for the electron donor material of material and with [6,6] phenyl-C61- methyl butyrate ([6,6]-phenyl-C61-
Butyric acid methyl ester, PCBM) be material electron acceptor material.
Metallic aluminum is prepared using vacuum evaporation technology on active layer, metallic aluminum obtains organic sun as negative electrode
Can battery device Q2.
Comparative example 1
Organic solar batteries device Q3 is prepared using method same as Example 3, the difference is that in active layer
Conjugated polymer be following structure of the prior art polymer,
N=10.
Comparative example 2
Organic solar batteries device Q4 is prepared using method same as Example 3, the difference is that in active layer
Conjugated polymer be following structure of the prior art polymer,
N=15.
Testing example 3-4 and comparative example 1-2 polymer solar is distinguished using Keithley236 Current Voltages source-measuring system
The performance of battery device, test result is shown in Table 1.
Table 1：
| Solar cell device | Short circuit current flow (mA/cm2) | Open-circuit voltage (V) | Energy conversion efficiency (%) |
| The Q1 of embodiment 3 | 5.11 | 0.55 | 1.25 |
| The Q2 of embodiment 4 | 5.13 | 0.52 | 1.21 |
| The Q3 of comparative example 1 | 4.96 | 0.49 | 1.12 |
| The Q4 of comparative example 2 | 4.85 | 0.50 | 1.08 |
As seen from the data in Table 1, due to using the electrophilic construction unit and electron knot in the present invention with specific structure
The combination of structure unit, the polymer solar that embodiment 1-2 conjugated polymer is prepared as the electron donor material of active layer
Battery device Q1-Q2 energy conversion efficiency, hence it is evident that higher than the solar energy prepared using other conjugated polymers in the prior art
Battery device Q3-Q4.The solar cell device and the matching degree of solar spectrum that i.e. prepared by conjugated polymer of the invention are high,
Carrier mobility speed is high, can improve carrier and reach the ratio and charge collection efficiency of electrode, so as to improve energy conversion effect
Rate.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (6)
1. one kind is used for organic semi-conductor conjugated polymer, it is characterised in that general structure is as follows：
Wherein, n is the natural number between 10~100；R1For H or C1~C20Alkyl, R2For C1~C10Alkyl.
2. a kind of preparation method for organic semi-conductor conjugated polymer, it is characterised in that comprise the following steps：
Compound I and compound II with following structural formula are provided respectively：
Wherein, R1For H or C1~C20Alkyl, R2For C1~C10Alkyl；
Under protective gas atmosphere, anhydrous and oxygen-free environment, by the compound I and the compound II in organic solvent and catalysis
Agent carries out Stille coupling reactions under conditions of existing, wherein, the compound I and the compound II mol ratio are 1:
1.5~1.5:1, reaction temperature is 80 DEG C~100 DEG C, and the reaction time is 48h~72h, obtains having following knot after isolating and purifying
The conjugated polymer of structure formula：
Wherein, n is the natural number between 10~100.
3. the preparation method according to claim 2 for organic semi-conductor conjugated polymer, it is characterised in that described
The addition of catalyst is the 0.01%~5% of the molal quantity of the compound II；The catalyst is organic palladium and organic phosphine
The mixture of part.
4. the preparation method according to claim 3 for organic semi-conductor conjugated polymer, it is characterised in that described
In the mixture of organic palladium and organophosphorus ligand, the mol ratio of the organic palladium and the organophosphorus ligand is 1:5~1:10；Institute
Organic palladium is stated for three (dibenzalacetone) two palladium；The organophosphorus ligand is three (o-methyl-phenyl) phosphines.
5. the preparation method according to claim 2 for organic semi-conductor conjugated polymer, it is characterised in that described
Compound I is made by following steps：
Compound C and compound D with following structural formula are provided：
C:D:
Under conditions of protective gas atmosphere, -78 DEG C, in the organic solution that lithium diisopropyl amido is added to the compound C,
Wherein, the lithium diisopropyl amido and the compound C mol ratio are 1:1~1.5:1, stirring reaction 2h~3h, then
Compound D is added into above-mentioned system and carries out Wittig-Horner reactions, wherein, the compound D and the compound C's
Mol ratio is 1:2.0~1:Recover to room temperature to continue to react 12h~15h after 2.5 reaction 0.5h~1h, had after isolating and purifying
There is the compound E of following structural formula：
E:
Under conditions of protective gas atmosphere, -78 DEG C, in the organic solution that n-BuLi is added to the compound E, wherein,
The n-BuLi and the compound E mol ratio are 2.2:1~2.5:1, stirring reaction 2h~3h, then to above-mentioned system
Middle addition trimethyltin chloride, wherein, the trimethyltin chloride and the compound E mol ratio are 2.0:1~2.5:1,
Recover to room temperature to continue to react 20h~24h after reaction 0.5h~1h, obtain the compound I with following structural formula：
6. the preparation method according to claim 2 for organic semi-conductor conjugated polymer, it is characterised in that described
Compound II is made by following steps：
Compound F and compound G is provided, the structural formula of the compound F is：
The structural formula of the compound G is：
Wherein, R2For C1~C10Alkyl；And
In inert gas shielding atmosphere, the compound F and compound G are dissolved in the first solvent and obtain the first mixed liquor,
Catalyst and alkali are instilled into first mixed liquor, in stirring reaction 4 hours at 130 DEG C, describedization is obtained after isolating and purifying
Compound II；Wherein, the mole of the catalyst is the 10% of the mole of the compound F, the alkali and the compound G
Mol ratio be 1: 1；The mol ratio of the compound F and compound G are 1:2.
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