CN106589325A - Benzo[c]cinnoline containing conjugated polymer and synthesis method and application thereof - Google Patents
Benzo[c]cinnoline containing conjugated polymer and synthesis method and application thereof Download PDFInfo
- Publication number
- CN106589325A CN106589325A CN201611102108.7A CN201611102108A CN106589325A CN 106589325 A CN106589325 A CN 106589325A CN 201611102108 A CN201611102108 A CN 201611102108A CN 106589325 A CN106589325 A CN 106589325A
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- Prior art keywords
- polymer
- pzl
- dried
- conjugated
- benzo
- Prior art date
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 45
- SWJXWSAKHXBQSY-UHFFFAOYSA-N benzo(c)cinnoline Chemical compound C1=CC=C2C3=CC=CC=C3N=NC2=C1 SWJXWSAKHXBQSY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 229920000642 polymer Polymers 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920000144 PEDOT:PSS Polymers 0.000 claims abstract description 7
- 230000004044 response Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 87
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 58
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 56
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- 239000012043 crude product Substances 0.000 claims description 32
- 239000010410 layer Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 26
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003208 petroleum Substances 0.000 claims description 20
- 208000035126 Facies Diseases 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000012188 paraffin wax Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000004528 spin coating Methods 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 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 14
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 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 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- 229910003472 fullerene Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 230000007812 deficiency Effects 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- -1 pinacol boric acid ester Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 230000021615 conjugation Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000011737 fluorine Chemical group 0.000 claims description 5
- 229910052731 fluorine Chemical group 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 238000006619 Stille reaction Methods 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 230000002146 bilateral effect Effects 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 2
- GPPYYGWYUFOWSR-UHFFFAOYSA-N 1,3-dibromo-2-fluorobenzene Chemical compound FC1=C(Br)C=CC=C1Br GPPYYGWYUFOWSR-UHFFFAOYSA-N 0.000 claims description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical class BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000002798 polar solvent Substances 0.000 description 17
- 0 CCC(C)(C)c1cc2nnc(CC(*)C(*)=C3)c3c2cc1* Chemical compound CCC(C)(C)c1cc2nnc(CC(*)C(*)=C3)c3c2cc1* 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- HQOWCDPFDSRYRO-CDKVKFQUSA-N CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 Chemical compound CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 HQOWCDPFDSRYRO-CDKVKFQUSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000013087 polymer photovoltaic Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000009504 vacuum film coating Methods 0.000 description 2
- RDJGLLICXDHJDY-LLVKDONJSA-N (2r)-2-(3-phenoxyphenyl)propanoic acid Chemical compound OC(=O)[C@H](C)C1=CC=CC(OC=2C=CC=CC=2)=C1 RDJGLLICXDHJDY-LLVKDONJSA-N 0.000 description 1
- DKLWRIQKXIBVIS-UHFFFAOYSA-N 1,1-diiodooctane Chemical compound CCCCCCCC(I)I DKLWRIQKXIBVIS-UHFFFAOYSA-N 0.000 description 1
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical compound FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 description 1
- WMASLRCNNKMRFP-UHFFFAOYSA-N 1-fluoro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(F)=C1 WMASLRCNNKMRFP-UHFFFAOYSA-N 0.000 description 1
- LFCRAWFKWPESBM-UHFFFAOYSA-N 2,9-difluorobenzo[c]cinnoline Chemical class FC1=CC2=C(N=NC=3C=CC(=CC2=3)F)C=C1 LFCRAWFKWPESBM-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- LNZHAYNBUMVVBK-UHFFFAOYSA-N Fc1cc2n[s]nc2cc1 Chemical compound Fc1cc2n[s]nc2cc1 LNZHAYNBUMVVBK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VHHDKHOBNKXVNU-UHFFFAOYSA-N c1cc(c2n[s]nc2cc2)c2c2n[s]nc12 Chemical compound c1cc(c2n[s]nc2cc2)c2c2n[s]nc12 VHHDKHOBNKXVNU-UHFFFAOYSA-N 0.000 description 1
- ZPLSFSRPXNAVRR-UHFFFAOYSA-N c1cncc2n[s]nc12 Chemical compound c1cncc2n[s]nc12 ZPLSFSRPXNAVRR-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 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
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Abstract
The invention discloses a benzo[c]cinnoline containing conjugated polymer and a synthesis method and application of the benzo[c]cinnoline containing conjugated polymer. The invention refers to the structural formula of a benzo[c]cinnoline based conjugated polymer. The common OPVs device prepared by taking the benzo[c]cinnoline based conjugated polymer as photosensitive materials is high in open-circuit voltage, wide in spectral response range and strong in spectral response, ideal in fill factors and larger in short-circuit current density, wherein the structure of the device is ITO/PEDOT: PSS/Polymer: PC71BM/LiF/Al, and the energy conversion efficiency of the common OPVs device is as high as 7.92%, so that potentials in OPVs and good application prospects of the polymers are fully displayed.
Description
Technical field
The present invention relates to organic photovoltaic battery (OPVs) material and construction applications, and in particular to a kind of conjugated polymer and its
Preparation method and application.
Background technology
With social development make rapid progress, energy problem has become a more and more important topic, especially with
Solar energy, wind energy, water energy etc. are even more the focus that people explore and study for the clean energy resource of representative.Organic photovoltaic battery (OPVs)
It is a kind of device for converting the solar into electric energy by the use of organic/polymer semiconducting material as photoactive layer.With other classes
The solaode of type is compared, and low cost that OPVs has, light weight, processing technology are simple, can print on a large scale and flexibility etc.
Advantage, has shown huge commercial application prospect.The PCE of current organic solar batteries is more than 10%, but its photoelectricity
Transformation efficiency distance realizes that the requirement of commercial applications also has a certain distance.Want further to improve organic solar batteries
Performance, just must constantly explore new construction unit, and design and synthesize new solution for high-performance photovoltaic material with this.
Benzo [c] cinnolines (ZL) is a kind of nitrogen-containing heterocycle compound, and coplanarity is good, is used for based on the polymer of ZL
Organic field effect tube and organic light emission field.Jyh-Chien Chen et al. by the dialdehyde derivant of benzo [c] cinnolines with
Double phosphine esters of benzene carry out Huo Naer-Wordsworth-Ai Mengsi reactions, have successfully been obtained poly- with n-type carrier transmission characteristics
Compound, and it is prepared into organic field effect tube (Synthesis and properties of air-stable n-
channel semiconductors based on MEH-PPV derivatives containing benzo[c]
Cinnoline moieties, Journal of Materials Chemistry C, 2014,2,4835-4846)；Subsequently, he
By benzo [c] cinnolines and fluorenes copolymerization, the polymer of acquisition realizes the enhanced luminescence generated by light (UV- of ultraviolet radioactive
irradiation-enhanced photoluminescence emission of polyfluorenes containing
Heterocyclic benzo [c] cinnoline moieties, Macromolecules, 2015,48 (13), 4373-
4381).However, up to the present, yet there are no application of benzo [c] cinnolines in OPVs.The present invention is first by benzo [c] cinnolines
Introduce OPVs, meanwhile, in order to strengthen the intermolecular force of polymer, improve carrier mobility, reduce polymer HOMO,
Lumo energy, introduces two fluorine atoms on benzo [c] cinnolines, obtains 2,9- difluoro benzo [c] cinnolines conjugate units (DFZL),
Had not been reported based on the polymer of DFZL, be even more first for OPVs photovoltaic materials.
The content of the invention
In view of problem above, the present invention provide a kind of conjugated polymer based on benzo [c] cinnolines and preparation method thereof and
Application in OPVs.
The technical scheme is that：
A kind of conjugated polymer containing benzo [c] cinnolines, with below general formula (I)：
In formula I, X is hydrogen or fluorine；Ar is the conjugation aromatic derivatives containing alkyl side chain；Natural numbers of the n for 5-1000.
In formula I, Ar is the conjugation aromatic derivatives containing alkyl side chain, and its structural formula is as shown in formula II or formula III：
In formula II and formula III, R is the linear paraffin or branched paraffin that carbon number is 4-30；D is conjugated for electron rich
Construction unit；A is electron deficiency conjugated structure unit.
Conjugated structure units of the D in formula II for electron rich, its structure is listed below, but is not restricted to following formula institute
Row：
In the structural formula of above-mentioned each unit, R is the linear paraffin or branched paraffin that carbon number is 4-30.
Conjugated structure units of the A in formula III for electron deficiency, its structure is listed below, but is not restricted to following formula institute
Row：
In the structural formula of above-mentioned each unit, R is the linear paraffin or branched paraffin that carbon number is 4-30.
One kind in formula I is based on benzo [c] cinnoline derivatives and the conjugated polymer of electron rich conjugated structure unit (D)
PZL-D, its synthetic method：Both sides connect double bromine compoundss monomers (M1) of benzo [c] cinnoline derivatives of alkylthrophene and richness electricity
The bilateral tin reagent monomer (M2) of sub- conjugated structure cells D carries out the reaction of Stille coupling polymers and obtains, as follows：
In structure above, X is hydrogen or fluorine；R is the linear paraffin or branched paraffin that carbon number is 4-30.
One kind in formula I is based on benzo [c] cinnoline derivatives and the conjugated polymer of electron deficiency conjugated structure unit
PZL-A, its synthetic method：Connect using both sides alkylthrophene benzo [c] cinnoline derivatives double bromine compoundss monomer M1 with lack
Bilateral pinacol boric acid ester monomer M3 of electron conjugated structure unit A carries out the reaction of Suzuki coupling polymers and obtains, following institute
Show：
In structure above, X is hydrogen or fluorine；R is the linear paraffin or branched paraffin that carbon number is 4-30.
Above-mentioned both sides connect the preparation method of double bromine compoundss monomers (M1) of benzo [c] cinnoline derivatives of alkylthrophene,
As shown in formula (IV), (V), (VI)：
Wherein, the synthesis step of above-mentioned intermediate compound 1 is：1-10mmol is sequentially added in single necked round bottom flask is dried
1,4- dibromobenzenes (bis- bromo- 2- fluorobenzene of 1,4-), magnetic stir bar, 50-150mL weak polar solvents, 5-10mL trifluoroacetic acids,
10-60min is stirred under 10-20mL trifluoroacetic anhydride, ice bath.It is dividedly in some parts 2-20mmol NH4NO3Pressed powder, when solution becomes
Into orange, solution removing ice bath is reacted into 6-48 hours again.Reaction mixture is poured in 50-400mL distilled water, then with weak
Polar solvent extract, merges organic faciess and washes, and organic faciess are dried with anhydrous magnesium sulfate, after filtration, will be filtered with Rotary Evaporators
Solvent in liquid is spin-dried for obtaining crude product, and crude product crosses silicagel column (with petroleum ether/dichloromethane as eluant), obtains white solid
Body powder, as intermediate compound 1.
Weak polar solvent is dichloromethane, chloroform, ether, acetone, benzene, toluene, tetrahydrofuran etc..
The synthesis step of above-mentioned intermediate compound 2 is：The intermediate compound 1 of 1-10mmol is added toward reaction bulb first, then
10-30mmol copper powders are added, 20-100mL intensive polar solvents are eventually adding, 60-180 DEG C of reaction 1-12 under nitrogen protection, is warmed up to
Hour, then make reaction be cooled to room temperature, add 10-100mL toluene, and filter out remaining copper powder, then eaten with saturation
Salt water washing.Last organic layer anhydrous magnesium sulfate is dried and is spin-dried for, and finally with ethyl alcohol recrystallization, finally obtains during yellow crystals are
Between compound 2.
Intensive polar solvent is DMF, dimethyl sulfoxide, acetonitrile, methanol etc..
Preferably, the synthesis step of above-mentioned intermediate compound 3 is：1- is sequentially added in the good there-necked flask of clean dry
10mmol intermediate compounds 2,1-10mmol 4- alkyl -2- tributyl tins-thiophene, 0.01-1mmol palladium class catalyst and 10-
200mL weak polar solvents, then in N260-150 DEG C of lucifuge reaction 6-48h is warming up under protection.Question response mixture is cooled to
Extracted with weak polar solvent after room temperature, organic faciess are dried with anhydrous magnesium sulfate after washing again, filter, filtrate is spin-dried for into solvent
After obtain crude product, crude product carries out column chromatography by eluant of petroleum ether/dichloromethane, obtains yellow solid for middle chemical combination
Thing 3.
Weak polar solvent is dichloromethane, chloroform, ether, acetone, benzene, toluene, tetrahydrofuran etc..Palladium class catalyst is four
Triphenyl phosphorus palladium, three (dibenzalacetone) two palladium (0) etc..The synthesis step of above-mentioned intermediate compound 4 is：It is good in clean dry
There-necked flask in sequentially add 1-10mmol Lithium Aluminium Hydrides and 10-100mL weak polar solvents, in noble gases (such as nitrogen, argon
Gas) protection is lower flow back under conditions of slowly Deca 1-10mmol intermediate compound 3 and weak polar solvent mixed solution.Add
Afterwards, then the 1-10 hours that flow back, room temperature is cooled to, reaction mixture is extracted with weak polar solvent, and organic faciess are used after washing again
Anhydrous magnesium sulfate is dried, and filters, filtrate is spin-dried for crude product is obtained after solvent, and crude product is with petroleum ether/dichloromethane as eluting
Agent carries out column chromatography, obtains yellow solid for intermediate compound 4.
Weak polar solvent is dichloromethane, chloroform, ether, acetone, benzene, toluene, tetrahydrofuran etc..
The synthesis step of above-mentioned polymerized monomer M1 is：Add in the middle of 1-10mmol successively in the good there-necked flask of clean dry and change
Compound 4,20-200mL weak polar solvents so as to fully dissolve, then move on to condition of ice bath stirring 10-60min.It is slowly added into again
1-20mmol NBS, add, and reactant mixture is extracted with weak polar solvent, organic faciess
It is dried with anhydrous magnesium sulfate after washing again, filters, filtrate is spin-dried for crude product is obtained after solvent, crude product with petroleum ether is
Eluant carries out column chromatography purification, obtains yellow solid for monomer M1.
Weak polar solvent is dichloromethane, chloroform, ether, acetone, benzene, toluene, tetrahydrofuran etc..
The building-up process of the monomer M2 can be adopted with the following method：By the compound that 1-10mmol structures are D conjugate units
Be dissolved in solvent weak polar solvent, then at a temperature of -78～25 DEG C Deca n-BuLi (rate of charge of D and n-BuLi is 1:
0.5～4), reaction mixture is reacted 0.5～12 hour at a temperature of -78～25 DEG C, is subsequently adding trimethyltin chloride (D and three
The rate of charge of methyl chloride stannum is 1:0.5～4), react 0.5～12 hour；Add water termination, with nonpolar solvent extraction, washes,
It is dried, filters, be spin-dried for.The monomer M2 based on D6 is obtained with non-polar solven/recrystallizing methanol.
Weak polar solvent is dichloromethane, chloroform, ether, acetone, benzene, toluene, tetrahydrofuran etc..Non-polar solven is stone
Oily ether, normal hexane.
The building-up process of above-mentioned monomer monomer M3 can be adopted with the following method：The dibromo chemical combination of electron deficiency conjugated structure unit A
Thing is synthesized under conditions of being catalyst with double (diphenylphosphine) the ferrocene palladium chlorides of 1,1- with duplex pinacol borate, is seen
Formula (VII), its preparation method is as follows：
Described conjugated polymer PZL-D is obtained by the method synthesis of Stille coupling polymerizations, and its synthetic method is：Will
0.5mmol monomer M1 and 0.5mmol monomer M2 are dissolved in 2-20mL toluene, and nitrogen protection is lower to add 0.005-0.05mmol tetra-
(triphenyl phosphorus) palladium (or other palladium class catalyst), is warming up to 60-140 DEG C of reaction 6-48h, after being cooled to room temperature, uses CH3OH sinks
Drop, filtration gained solid filter paper parcel is placed in apparatus,Soxhlet'ses uses CH successively3OH, acetone, petroleum ether and CHCl3Extracting, institute
Obtain CHCl3Solution is spin-dried for, and vacuum drying obtains orange, red or atropurpureuss solid (according to electron rich conjugated structure unit
Architectural difference, color are different), as polymer P ZL-D.
The conjugated polymer PZL-A is synthesized by the method for Suzuki coupling polymerizations, and its synthetic method is：Will
The monomer M1 and 0.5mmol monomer M3 of 0.5mmol is dissolved in 2-20mL toluene under nitrogen protection, adds 0.005-0.05mmol
Four (triphenyl phosphorus) four (triphenyl phosphorus) palladium (or other palladium class catalyst), 1-10mL concentration are water-soluble for the potassium carbonate of 2mol/L
Liquid, is warming up to 60-140 DEG C of reaction 6-48h, after reaction terminates, is cooled to room temperature, uses CH3OH is settled, and filters gained solid filter
Paper bag is wrapped up in be placed in apparatus,Soxhlet'ses and uses CH successively3OH, acetone, petroleum ether and CHCl3Extracting, gained CHCl3Solution is spin-dried for, and
Vacuum drying obtains atropurpureuss, blue or green solid (according to the architectural difference of electron deficiency conjugated structure unit, color is different),
As polymer P ZL-A.
The conjugated polymer based on benzo [c] cinnolines of the present invention is specially polymer shown in following formula P1-P6.
Described formula I polymer, as shown in Figure 6 and Figure 7, is applied to preparation forward direction OPVs devices and reverse
OPVs devices.Positive OPVs devices and reverse OPVs devices are as shown below, wherein, anode modification layer is PEDOT：PSS or
MoO3, photoactive layer are polymer (PZL-D or PZL-A)/PCBM or polymer (PZL-D or PZL-A)/non-fullerene electronics
Acceptor material；Cathodic modification layer is LiF, PFN, calcium etc.；Metal is aluminum or silver.
The preparation process of described positive OPVs devices is：The spin coating on ITO (tin indium oxide) electro-conductive glass of wash clean
PEDOT/PSS solution (2000rpm, time are 30s), toasts 10-30 minutes in being then placed on baking oven at a temperature of 150 DEG C
(or MoO3 of one layer of 10-30nm thickness of evaporation), then by polymer (PZL-D or PZL-A)/fullerene derivate or polymerization
The solution spin coating of thing (PZL-D or PZL-A)/non-fullerene electron acceptor material thereon as photoactive layer (mixed solution
Spin coating speed is 600-4000rpm), then in the PFN of one layer of 2-15nm of photoactive layer spin coating, or evaporation 0.2-0.8nm
LiF, or the calcium of 5-30nm, are then deposited with the metallic aluminium or silver of 50-150nm again.So as to prepare positive OPVs devices.
The preparation process of described reverse OPVs devices is：The spin coating on ITO (tin indium oxide) electro-conductive glass of wash clean
The PFN of one layer of 2-15nm, then by polymer (PZL-D or PZL-A)/fullerene derivate or polymer (PZL-D or PZL-
Used as photoactive layer, (the spin coating speed of mixed solution is 600- thereon for the solution spin coating of A)/non-fullerene electron acceptor material
4000rpm), then in photoactive layer one layer of 5-20nm MoO3 is deposited with, is finally deposited with the metallic aluminium or silver of 50-150nm.So as to make
It is standby to obtain reverse OPVs devices.
Benzo [c] cinnolines is introduced OPVs by the present invention first, meanwhile, in order to strengthen the intermolecular force of polymer, carry
High carrier mobility, reduces HOMO, the lumo energy of polymer, introduces two fluorine atoms, obtain 2 on benzo [c] cinnolines,
9- difluoro benzo [c] cinnolines conjugate units (DFZL), is had not been reported based on the polymer of DFZL, for OPVs photovoltaic materials more
It is first.
Most common organic sun prepared by with the conjugated polymer based on benzo [c] cinnolines of the present invention as light-sensitive material
Can battery (OPVs) device (device architecture is：ITO/PEDOT：PSS/Polymer：PC71BM/LiF/Al), its open-circuit voltage is high,
Spectral response range width and it is strong, fill factor, curve factor is preferable, and short-circuit current density is larger, and its energy conversion efficiency is up to 7.92%, work
Skill low cost and environmental friendliness, fully present potentiality and applications well prospect in OPVs.
Description of the drawings
Fig. 1 is the thermal gravimetric analysis curve that embodiment prepares gained P1P2P3P5P6 conjugated polymers.
Fig. 2 is that embodiment prepares gained ultra-violet absorption spectrum of the P1P2P3P5P6 conjugated polymers in chloroformic solution.
Fig. 3 is the cyclic voltammetry curve that embodiment prepares gained P1P2P3P5P6 conjugated polymers.
Fig. 4 is that embodiment prepares gained P1P2P3P5P6 conjugated polymers and P71The electric current of photoelectric device is made in CBM blendings
Density (J)-voltage (V) curve.
Fig. 5 is that embodiment prepares gained P3 and ultra-violet absorption spectrums of the ITIC in chloroformic solution.
Fig. 6 is the structure chart of positive OPVs devices.
Fig. 7 is the structure chart of reverse OPVs devices.
Fig. 8 polymer photovoltaics performances.
Specific embodiment
With reference to specific embodiment, the present invention will be further described, but the present invention and be only not limited to following examples
Described structure.
Embodiment 1
Synthesis based on the conjugated polymer (P1) of benzo [c] cinnolines
The preparation method of intermediate 1 (the fluoro- 5- Nitrobenzol of-two bromo- 2- of Isosorbide-5-Nitrae), is carried out according to aforesaid equation, its concrete behaviour
As：- two bromo- 2- fluorobenzene of (5.0g, 19.70mmol) Isosorbide-5-Nitrae, magnetic force are sequentially added in 100mL is dried single necked round bottom flask to stir
Son, 30mL dichloromethane (DCM), 8mL trifluoroacetic acids (TFA), 16mL trifluoroacetic anhydride (TFAA) are mixed, under ice bath, 30min is stirred.
It is dividedly in some parts ammonium nitrate (2.0g, 25.0mmol) pressed powder.Continue 24h under room temperature reaction after adding.Solution is poured into
In 100mL distilled water, then extracted with dichloromethane, merge organic faciess, organic faciess are dried with anhydrous magnesium sulfate, after filtration, will
Filtrate rotation solvent evaporated obtains crude product, and crude product adopts silicagel column (petroleum ether is eluant) to carry out column chromatography, obtains white
Color pressed powder is intermediate 1, yield 85%.1H NMR(400MHz,CDCl3,δ/ppm):8.19-8.18 (d, J=
5.43Hz, 1H), 7.54-7.53 (d, J=6.85Hz, 1H).
The preparation method of intermediate 2, is carried out according to aforesaid equation, and its concrete operations is：In first adding toward reaction bulb
Mesosome 1 (5.0g, 16.73mmol), adds copper powder (1.4g, 22.02mmol) and is eventually adding 60mL DMFs
(DMF) system is inserted three hours of reaction in 120 degree of baths, is then cooled to room temperature, adds 30mL by, nitrogen charging gas shielded
Toluene, filters out remaining copper powder, and then organic faciess saturated common salt water washing is dried with anhydrous magnesium sulfate, after filtration, will filter
Solvent in liquid is spin-dried for obtaining crude product, and crude product ethyl alcohol recrystallization finally obtains yellow crystals and is intermediate 2, yield
46%.1H NMR(400MHz,CDCl3,δ/ppm):8.56-8.54 (d, J=6.07Hz, 2H), 7.08-7.06 (d, J=
7.53Hz,2H).
Intermediate 3-C6C8Preparation method, carry out according to aforesaid equation, its concrete operations is：It is good in clean dry
Intermediate compound 2 (2g, 4.57mmol), 2- (tributyl tinbase) -4- (2- hexyl certain herbaceous plants with big flowers bases) thiophene are sequentially added in there-necked flask
(6g, 10.5mmol), Pd (PPh3)4(0.20g, 0.18mmol) and 100mL newly steam toluene, then in N2110 are warming up under protection
DEG C reaction 30h.Reaction system is cooled to room temperature, then with using CH2Cl2Anhydrous magnesium sulfate is used in extraction, organic faciess after washing again
It is dried, filters, filtrate is spin-dried for crude product is obtained after solvent, crude product carries out post layer by eluant of petroleum ether/dichloromethane
Analysis, obtains yellow solid and is intermediate 3-C6C8, yield 80.1%.1H NMR(400MHz,CDCl3,δ/ppm):8.55-
(8.53 d, J=6.89Hz, 2H), 7.43 (s, 2H), 7.11 (s, 2H), 7.08 (s, 2H), 7.07 (s, 2H) 2.60-2.58 (d, J
=6.68Hz, 4H), 1.64-1.59 (t, 1H), 1.37-1.26 (m, 48H), 0.93-0.85 (m, 12H).
Intermediate 4-C6C8Preparation method, carry out according to aforesaid equation, its concrete operations is：It is good in clean dry
Lithium aluminium hydride reduction (0.61g, 16.00mmol) is sequentially added in there-necked flask and 70mL newly steams ether, lead to the N of 30min2Stream, then in N2
Protection is lower flow back under conditions of slowly Deca intermediate 3-C6C8The mixed solution of (1.79g, 2.00mmol) and benzene.Behind adding
React 2h under conditions of backflow again, reaction system uses CH after being cooled to room temperature2Cl2Nothing is used in extraction, organic faciess after washing again
Water magnesium sulfate is dried, and filters, filtrate is spin-dried for crude product is obtained after solvent, and crude product is with petroleum ether/dichloromethane as eluant
Column chromatography is carried out, yellow solid is obtained and is intermediate 4-C6C8, yield 79%.1H NMR(400MHz,CDCl3,δ/ppm):
9.01-8.99 (d, J=7.43Hz, 2H), 8.10-8.07 (d, J=11.37Hz, 2H), 7.56 (s, 2H), 7.09 (s, 2H),
2.64-2.62 (d, J=6.64Hz, 2H), 1.68 (s, 2H), 1.31-1.27 (m, 48H), 0.88-0.85 (m, 12H)
Monomer M1-C6C8Preparation method, carry out according to aforesaid equation, its concrete operations is：It is good in clean dry
Add intermediate compound intermediate 4-C in 250mL there-necked flasks successively6C8(0.83g, 1.00mmol), chloroform so as to fully molten
Solution, then moves on to condition of ice bath stirring 30min.N-bromosuccinimide (0.38g, 2.1mmol) is slowly added into again, after adding
Face again at room temperature react under overnight, after having reacted, use CH2Cl2Extraction, organic faciess are dry with anhydrous magnesium sulfate again after washing
It is dry, filter, filtrate is spin-dried for crude product is obtained after solvent, crude product carries out column chromatography purification by eluant of petroleum ether, obtains
Yellow solid is monomer M1-C6C8, yield 80%.1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89 (d, J=
6.13Hz, 2H), 8.06-8.03 (d, J=11.02Hz, 2H), 7.40 (s, 2H), 7.09 (s, 2H), 2.58-2.56 (d, J=
6.03Hz,2H),1.73(s,2H),1.31-1.27(m,48H),0.88-0.85(m,12H)。
The preparation method of conjugated polymer P1, is carried out according to aforesaid equation, and its concrete operations is：Toward the there-necked flask of 50mL
Middle addition M1-C6C8(0.20g, 0.2mmol), M3-A1 (0.16g, 0.2mmol), 10mL toluene, lead to nitrogen 15 minutes, add four
(triphenyl phosphorus) palladium (4.6mg, 0.004mmol) and 4mL concentration are the wet chemical of 2M, are warming up to 110 DEG C of stirring reactions
After 48 hours, after reaction terminates, room temperature is cooled to, the solution after having reacted is added drop-wise in 200mL methanol, then sucking filtration, received
Collection black solid.Then methanol (12h), acetone (12h), normal hexane (12h), chloroform are used successively using apparatus,Soxhlet'ses
(12h) extract, the chloroform extraction liquid of polymer is spin-dried for, obtain atropurpureuss polymer solids and be polymer P 1.
Embodiment 2
Synthesis based on the conjugated polymer (P2) of benzo [c] cinnolines
Intermediate 3-C8C10Preparation method, carry out according to aforesaid equation, its concrete operations is：It is good in clean dry
Intermediate compound 2 (2g, 4.57mmol), 2- (tributyl tinbase) -4- (2- octyl group certain herbaceous plants with big flowers bases) thiophene are sequentially added in there-necked flask
(6.86g, 10.5mmol), Pd (PPh3)4(0.21g, 0.18mmol) and 100mL newly steam toluene, then in N2It is warming up under protection
110 DEG C of reaction 30h.Reaction system is cooled to room temperature, then with using CH2Cl2Anhydrous sulfur is used in extraction, organic faciess after washing again
Sour magnesium is dried, and filters, filtrate is spin-dried for crude product is obtained after solvent, and crude product is carried out by eluant of petroleum ether/dichloromethane
Column chromatography, obtains yellow solid and is intermediate 3-C8C10, yield 80.1%.1H NMR(400MHz,CDCl3,δ/ppm):
8.55-8.53 (d, J=6.89Hz, 2H), 7.43 (s, 2H), 7.11 (s, 2H), 7.08 (s, 2H), 7.07 (s, 2H) 2.60-
2.58 (d, J=6.68Hz, 4H), 1.64-1.59 (m, 1H), 1.37-1.26 (m, 64H), 0.93-0.85 (m, 12H).
Intermediate 4-C6C8Preparation method, carry out according to aforesaid equation, its concrete operations is：It is good in clean dry
Lithium aluminium hydride reduction (0.68g, 18.00mmol) is sequentially added in there-necked flask and 70mL newly steams ether, lead to the N of 30min2Stream, then in N2
Protection is lower flow back under conditions of slowly Deca intermediate 3-C8C10The mixed solution of (1.90g, 2.00mmol) and benzene.Behind adding
React 2h under conditions of backflow again, reaction system uses CH after being cooled to room temperature2Cl2Nothing is used in extraction, organic faciess after washing again
Water magnesium sulfate is dried, and filters, filtrate is spin-dried for crude product is obtained after solvent, and crude product is with petroleum ether/dichloromethane as eluant
Column chromatography is carried out, yellow solid is obtained and is intermediate 4-C8C10, yield 79%.1H NMR(400MHz,CDCl3,δ/ppm):
9.01-8.99 (d, J=7.43Hz, 2H), 8.10-8.07 (d, J=11.37Hz, 2H), 7.56 (s, 2H), 7.09 (s, 2H),
2.64-2.62 (d, J=6.64Hz, 2H), 1.68 (m, 2H), 1.31-1.27 (m, 64H), 0.88-0.85 (m, 12H).
Monomer M1-C8C10Preparation method, carry out according to aforesaid equation, its concrete operations is：It is good in clean dry
Add intermediate compound intermediate 4-C in 250mL there-necked flasks successively8C10(0.94g, 1.00mmol), chloroform so as to fully molten
Solution, then moves on to condition of ice bath stirring 30min.N-bromosuccinimide (0.37g, 2.1mmol) is slowly added into again, after adding
Face again at room temperature react under overnight, after having reacted, use CH2Cl2Extraction, organic faciess are dry with anhydrous magnesium sulfate again after washing
It is dry, filter, filtrate is spin-dried for crude product is obtained after solvent, crude product carries out column chromatography purification by eluant of petroleum ether, obtains
Yellow solid is monomer M1-C8C10, yield 80%.1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89 (d, J=
6.13Hz, 2H), 8.06-8.03 (d, J=11.02Hz, 2H), 7.40 (s, 2H), 2.58-2.56 (d, J=6.03Hz, 2H),
1.73(m,2H),1.31-1.27(m,64H),0.88-0.85(m,12H)。
The preparation method of conjugated polymer P2, is carried out according to aforesaid equation, and its concrete operations is：Toward the there-necked flask of 50mL
Middle addition M1-C8C100.2mmol each with M2-D1, after being dissolved in the solvent of toluene (6mL), nitrogen protection is lower to add four (triphens
Base phosphorus) palladium (4.62mg 0.004mmol), 110 DEG C of stirring reactions are warming up to after 48 hours, after reaction terminates, be cooled to room temperature,
Solution after having reacted is added drop-wise in 50mL methanol, then sucking filtration, collects black solid.Then using apparatus,Soxhlet'ses successively
With methanol (12h), acetone (12h), normal hexane (12h), chloroform (12h) extracting, by the chloroform extraction liquid of polymer
It is spin-dried for, obtains atropurpureuss polymer solids and be polymer P 2.Yield 57%, GPC：Mn=21.8kDa, Mw/Mn=2.4,1H
NMR(400MHz,CDCl3,δ/ppm):8.90-8.89 (br, J=6.13Hz, 2H), 8.06-8.03 (br, J=11.02Hz,
2H), 7.56 (br, 2H), 7.09 (s, 2H), 2.58-2.93 (br, J=6.03Hz, 2H), 1.11-1.97 (m, 64H), 0.88-
0.85(m,12H)。
Embodiment 3
Synthesis based on the conjugated polymer (P3) of benzo [c] cinnolines
The preparation method of conjugated polymer P3, is carried out according to aforesaid equation, and its concrete operations is：Take monomer M1-C8C10
0.2mmol each with M2-D3, is dissolved in toluene (6mL), and four (triphenyl phosphorus) palladium (4.62mg is added under nitrogen protective condition
0.004mmol), then stop after polymerization 24h at a temperature of refluxing toluene.Polymer solution is cooled to into room temperature, slowly heavy
Form sediment in methanol (50mL), the solid polymer of Precipitation uses methanol in apparatus,Soxhlet'ses successively, normal hexane, acetone, two
Chloromethanes, chloroform carry out drawer.Finally chloroform extraction drop is added in methanol, is filtered, will be the solid for being obtained true
Red brown solid powder is obtained after sky is drying for one day and is polymer P 3, yield 69%, GPC：Mn=24.8kDa, Mw/Mn=
2.1,1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89 (br, J=6.13Hz, 2H), 8.06-8.03 (br, J=
11.02Hz, 2H), 7.56 (br, 2H), 6.09 (br, 4H), 2.58-2.93 (br, J=6.03Hz, 2H), 1.11-1.97 (m,
64H),0.88-0.85(m,12H)。
Embodiment 4
Synthesis based on the conjugated polymer (P4) of benzo [c] cinnolines
Carry out according to above-mentioned reaction equation, take monomer M1-C8C100.2mmol each with M2-D4, is dissolved in toluene
(6mL), after, four (triphenyl phosphorus) palladium (4.62mg 0.004mmol) is added under nitrogen protection, then at a temperature of refluxing toluene
Stop after polymerization 24h.Polymer solution is cooled to into room temperature, being deposited in methanol (50mL) slowly, the solid of Precipitation
Polymer uses methanol in the apparatus,Soxhlet'ses successively, normal hexane, acetone, dichloromethane, and chloroform is extracting.Finally by trichlorine
Methane extracting solution is added drop-wise in methanol, after the filtering residue after filtration is vacuum dried one day, is obtained red brown solid powder and is formula
Polymer shown in P5, as polymer solubility is too poor, does not do dependence test.
Embodiment 5
Synthesis based on the conjugated polymer (P5) of benzo [c] cinnolines
Carry out according to above-mentioned reaction equation, take monomer M1-C6C80.2mmol each with M2-D8, is dissolved in toluene (6mL)
Afterwards, four (triphenyl phosphorus) palladium (4.62mg 0.004mmol) is added under nitrogen protection, be then polymerized at a temperature of refluxing toluene
Stop after 24h.Polymer solution is cooled to into room temperature, being deposited in methanol (50mL) slowly, the solid polymerization of Precipitation
Thing uses methanol in the apparatus,Soxhlet'ses successively, normal hexane, acetone, dichloromethane, and chloroform is extracting.Finally by chloroform
Extracting solution is added drop-wise in methanol, after the filtering residue after filtration is vacuum dried one day, is obtained red brown solid powder and is formula P5 institute
Show polymer, yield 76%, GPC：Mn=26.8kDa, Mw/Mn=2.8,1H NMR(400MHz,CDCl3,δ/ppm):8.90-
8.89 (br, J=6.13Hz, 2H), 8.06-8.03 (br, J=11.02Hz, 2H), 8.03 (s, 2H), 7.54 (s, 4H), 7.02
(s, 4H), 8.21-6.67 (br, 6H), 2.58-2.93 (br, J=6.03Hz, 2H), 1.11-1.97 (m, 64H), 0.88-0.85
(m,12H)。
Embodiment 6
Synthesis based on the conjugated polymer (P6) of benzo [c] cinnolines
Carry out according to above-mentioned reaction equation, take monomer M1-C6C80.2mmol each with M2-D9, is dissolved in toluene
(6mL) four (triphenyl phosphorus) palladium (4.62mg 0.004mmol) is then added under nitrogen protection, by reactant liquor in refluxing toluene
At a temperature of be polymerized 24h after stop.Polymer solution is cooled to into room temperature, being added drop-wise in methanol (50mL) slowly, Precipitation
Solid polymer use methanol in the apparatus,Soxhlet'ses successively, normal hexane, acetone, dichloromethane, chloroform is extracting.Finally
Chloroform extraction drop is added in methanol, the filtering residue after filtration obtains red brown solid powder after being vacuum dried one day and is
Polymer shown in formula P6, yield 88%, GPC：Mn=39.6kDa, Mw/Mn=2.0,1H NMR(400MHz,CDCl3,δ/ppm):
8.90-8.89 (br, J=6.13Hz, 2H), 8.06-8.03 (br, J=11.02Hz, 2H), 8.03 (s, 2H), 7.54 (s, 4H),
7.02 (s, 4H), 8.21-6.67 (br, 6H), 2.58-2.93 (br, J=6.03Hz, 2H), 1.11-1.97 (m, 64H), 0.88-
0.85(m,12H)。
Embodiment 7
The dissolubility of Inventive polymers and film property test
Polymer P 1, P2, P3, P5, P6 prepared by the present embodiment 1,2,3,5,6 is placed in common solvent, such as chlorobenzene, 1,
2- dichloro-benzenes, chloroform, toluene, trichloro-benzenes, methanol, normal hexane, petroleum ether, acetone etc., find polymer P 1, P2, P3, P5, P6
There is preferable dissolubility in chlorobenzene, 1,2- dichloro-benzenes, chloroform, toluene, trichloro-benzenes, and do not dissolve in methanol, normal hexane, oil
Ether, acetone.Polymer P 4 prepared by the present embodiment 4 cannot be dissolved in chlorobenzene, 1,2- dichloro-benzenes, chloroform, toluene, trichloro-benzenes, tetrahydrochysene
Furan equal solvent, this is likely due to the excessive reason of molecular weight.Therefore, polymer P 4 does not characterize other performance.
Embodiment 8
With the thermal stability of thermogravimetic analysis (TGA) test polymer
Polymer P 1, P2, P3, P5, P6 is placed in TA companies of U.S. Q50 thermogravimetric analyzers, under nitrogen atmosphere, lifting
Warm speed is 20 DEG C/min, and test temperature region is the heat decomposition temperature of test polymer under 50～700 DEG C of test conditions.Its survey
Examination curve is shown in Fig. 1.
Embodiment 9
With the absorbing ability of ultraviolet-visible spectrometer test polymer
Polymer P 1, P2, P3, P5, P6 is dissolved in chloroform, is surveyed using PE Lamda25 types ultraviolet-visual spectrometer
The absorbance of examination solution.Its absorption spectrum is shown in Fig. 2.
Embodiment 10
With the electrochemistry energy level and energy gap of electrochemical workstation test polymer
Polymer P 1, P2, P3, P5, P6 is dissolved in chloroform, is added drop-wise on ITO electro-conductive glass, treat that solvent is evaporated completely
Afterwards, just become working electrode, be to electrode, Ag/AgNO with metal platinum filament3Electrode as reference electrode, with tetra- fourths of 0.1mol/L
The acetonitrile solution of base hexafluorophosphoric acid amine is electrolyte solution, is polymerized using determining on ZAHNER ZENNIUM type electrochemical workstations
The cyclic voltammetric spectrogram (scanning speed is 100mV/s) of thing thin film, its cyclic voltammetric spectrogram are shown in Fig. 3.
Embodiment 11
With polymer shown in formula P1 as Polymer photovoltaic materials, positive organic solar batteries (OPVs) device of preparation (
Referred to as polymer solar battery PSCs), its device architecture is shown in Fig. 6, and its detailed process is as follows.
Ito glass is carried out with ITO abluents, deionized water, acetone, ethanol, isopropanol that concentration is 5% or so successively
Ultrasound wave cleans (each 30 minutes).After ito glass dries, processed 5 minutes with UV ozone, then by PEDOT:PSS with
The rotating speed of 4000rpm is spun on ito glass, is subsequently placed in 150 DEG C of high temperature oven, toasts 15min so that
PEDOT:The solvent and moisture of PSS surface residuals is able to fully removing (its thickness is 30～40nm).By obtained in the present invention
Polymer P 1 and PC71BM is with weight ratio as 1:1 blending is dissolved in dichloro-benzenes (concentration：15mg/mL), and add the 1,8- of 2vol%
Diiodo-octane.The active layer solution of above-mentioned blending is revolved into Tu to being covered with PEDOT:(active layer thickness on the ito glass of PSS thin layers
About 100nm), transfer it in vacuum film coating chamber, treat reduced pressure in vacuum coating room to 4 × 10-4Pa, evaporation
0.5nm thick lithium fluoride, then the metallic aluminium of about 100nm is deposited with, so as to prepare the positive sun based on P1 conjugated polymers
Can battery device (device architecture is：ITO/PEDOT：PSS/Polymer：P71CBM/LiF/Al).Using AAA level sun optical analogs
Device simulation obtains AM 1.5G sunlight (100mW/cm2), the solar cell device of preparation is placed in into AM 1.5G simulated solars
Irradiate under light, electric current density (J)-voltage (V) curve of OPVs devices is recorded with digital sourcemeter, so as to obtain opening for OPVs devices
Road voltage (Voc), short-circuit current density (Jsc), the photovoltaic parameter such as fill factor, curve factor (FF) and energy conversion efficiency (PCE).Its photovoltaic
Parameter is listed in table 1, and its J-V curve is shown in Fig. 4.
Embodiment 12
With polymer shown in formula P2, P3, P5, P6 as Polymer photovoltaic materials, with reference to OPV device architectures and system based on P1
Preparation Method prepares forward direction OPVs devices.Its photovoltaic parameter is listed in table 1, and its J-V curve is shown in Fig. 4.
Embodiment 13
With polymer shown in formula P3 as Polymer photovoltaic materials, with reference to the OPV device architectures (Fig. 6) based on P1 and preparation side
Method prepares the OPVs devices of polymer/non-fullerene system.By the obtained polymer P 3 and non-fullerene acceptor of the present invention
ITIC is with weight ratio as 1:1 blending is dissolved in dichloro-benzenes (P3 is shown in Fig. 5 with ITIC UV-visible spectrums in the solution).Will
The active layer solution of above-mentioned blending revolves Tu to being covered with PEDOT:On the ito glass of PSS thin layers (active layer thickness is about 100nm),
Transfer it in vacuum film coating chamber, treat reduced pressure in vacuum coating room to 4 × 10-4Pa, is deposited with the thick fluorine of 0.5nm
Change lithium, then the metallic aluminium of about 100nm is deposited with, so as to prepare the positive solar cell device based on P3 conjugated polymers
(device architecture is：ITO/PEDOT：PSS/P3：ITIC/LiF/Al).AM is obtained using the simulation of AAA levels solar simulator
1.5G sunlight (100mW/cm2), the solar cell device of preparation is placed under AM 1.5G simulated solar irradiations and is irradiated, use number
The electric current density (J) of word source table record OPVs devices-voltage (V) curve, so as to obtain the V of OPVs devicesoc、Jsc, FF and PCE
Deng photovoltaic parameter.Its photovoltaic parameter is listed in Fig. 8.
Claims (14)
1. one kind contains the conjugated polymer of benzo [c] cinnolines, and its structure is formula I：
Wherein, X is hydrogen or fluorine；Ar is the conjugation aromatic derivatives containing alkyl side chain.
2. conjugated polymer as claimed in claim 1, it is characterised in that the structural formula of Ar is formula II or formula III：
Wherein, R be linear paraffin, branched paraffin；D is electron rich conjugated structure unit；A is electron deficiency conjugated structure unit.
3. based on benzo [c] cinnoline derivatives and the conjugated polymer (PZL-D) of electron rich conjugated structure unit, which synthesizes one kind
Method：Double bromine compoundss monomers (M1) and the electron rich conjugation knot of benzo [c] cinnoline derivatives of alkylthrophene are connect using both sides
The bilateral tin reagent monomer (M2) of structure cells D carries out the reaction of Stille coupling polymers and obtains：
4. conjugated polymer (PZL-D) according to claim 3, it is characterised in that by the method for Stille coupling polymerizations
Synthesis obtains conjugated polymer PZL-D, and its synthetic method is：0.5mmol monomers (M1) and 0.5mmol monomers (M2) are dissolved in
2-20mL toluene, nitrogen protection is lower to add 0.005-0.05mmol tetra- (triphenyl phosphorus) palladium (or other palladium class catalyst), rises
Temperature uses CH to 60-140 DEG C of reaction 6-48h after being cooled to room temperature3OH is settled, and filtration gained solid filter paper parcel is placed in Soxhlet and carries
CH is used successively in taking device3OH, acetone, petroleum ether and CHCl3Extracting, gained CHCl3Solution is spin-dried for, and vacuum drying obtain it is orange,
Red or atropurpureuss solid, as polymer P ZL-D.
5. the conjugated polymer according to any one of claim 2-4, wherein the conjugated structure cells D of electron rich, its knot
Structure includes but is not limited to any one in having structure：
Wherein, R is linear paraffin or branched paraffin.
6. based on benzo [c] cinnoline derivatives and the conjugated polymer (PZL-A) of electron deficiency conjugated structure unit, which synthesizes one kind
Method：Double bromine compoundss monomers (M1) and the electron deficiency conjugation knot of benzo [c] cinnoline derivatives of alkylthrophene are connect using both sides
The bilateral pinacol boric acid ester monomer (M3) of structure unit A carries out the reaction of Suzuki coupling polymers and obtains：
7. conjugated polymer (PZL-A) according to claim 6, it is characterised in that by the method for Suzuki coupling polymerizations
Synthesis of conjugate polymer P ZL-A, its synthetic method is：The monomer (M1) and 0.5mmol monomers (M3) of 0.5mmol are dissolved in into 2-
In 20mL toluene under nitrogen protection, addition 0.005-0.05mmol tetra- (triphenyl phosphorus) four (triphenyl phosphorus) palladium (or other palladiums
Class catalyst), wet chemical of the 1-10mL concentration for 2mol/L is warming up to 60-140 DEG C of reaction 6-48h, and reaction terminates
Afterwards, room temperature is cooled to, uses CH3OH is settled, and filtration gained solid filter paper parcel is placed in apparatus,Soxhlet'ses uses CH successively3OH, third
Ketone, petroleum ether and CHCl3Extracting, gained CHCl3Solution is spin-dried for, and vacuum drying obtains atropurpureuss, blue or green solid, i.e.,
For polymer P ZL-A.
8. the conjugated polymer according to any one of claim 2,6 or 7, wherein the conjugated structure unit A of electron deficiency, its
Structure includes but is not limited to any one in having structure：
Wherein, R is linear paraffin, branched paraffin.
9. a kind of both sides connect the preparation method of double bromine compoundss monomers (M1) of benzo [c] cinnoline derivatives of alkylthrophene, should
Method is comprised the following steps：
(1) 1,4- dibromobenzenes (bis- bromo- 2- fluorobenzene of 1,4-), the magnetic force of 1-10mmol are sequentially added in single necked round bottom flask is dried
Stirrer, 50-150mL dichloromethane, 5-10mL trifluoroacetic acids, 10-20mL trifluoroacetic anhydride, stir 10-60min under ice bath.
It is dividedly in some parts 2-20mmol NH4NO3Solution removing ice bath, when solution becomes orange, is reacted 6-48 hours by pressed powder again.Will
Reaction mixture is poured in 50-400mL distilled water, is then extracted with dichloromethane, is merged organic faciess and is washed, organic faciess nothing
Water magnesium sulfate is dried, and after filtration, is spin-dried for obtaining crude product by the solvent in filtrate with Rotary Evaporators, and crude product crosses silicagel column
(with petroleum ether/dichloromethane as eluant), obtains white solid powder, as intermediate compound (Y1).
(2) intermediate compound (Y1) of 1-10mmol is added toward reaction bulb, 10-30mmol copper powders is added, is eventually adding 20-
100mL DMFs, are warmed up to 60-180 DEG C of reaction 1-12 hour, are then cooled to reaction under nitrogen protection
Room temperature, adds 10-100mL toluene, and filters out remaining copper powder, then use saturated common salt water washing.Last organic layer is used
Anhydrous magnesium sulfate is dried and is spin-dried for, and finally with ethyl alcohol recrystallization, finally obtains yellow crystals for intermediate compound (Y2).
(3) 1-10mmol intermediate compounds (Y2) are sequentially added in the good there-necked flask of clean dry, 1-10mmol 4- alkyl-
2- tributyl tins-thiophene, 0.01-1mmol Pd (PPh3)4With 10-200mL toluene, then in N260-150 is warming up under protection
DEG C lucifuge reaction 6-48h.Question response mixture is extracted with dichloromethane after being cooled to room temperature, and organic faciess use nothing after washing again
Water magnesium sulfate is dried, and filters, filtrate is spin-dried for crude product is obtained after solvent, and crude product is with petroleum ether/dichloromethane as eluant
Column chromatography is carried out, and yellow solid is obtained for intermediate compound Y3.
(4) 1-10mmol Lithium Aluminium Hydrides are sequentially added in the good there-necked flask of clean dry and 10-100mL newly steams toluene, lazy
Property gas (such as nitrogen, argon) protection is lower flow back under conditions of slowly Deca 1-10mmol intermediate compound (Y3) and benzene mixing
Solution.After adding, then the 1-10 hours that flow back, room temperature is cooled to, reaction mixture is extracted with dichloromethane, and organic faciess are through washing
It is dried with anhydrous magnesium sulfate again afterwards, filters, filtrate is spin-dried for crude product is obtained after solvent, crude product is with petroleum ether/dichloromethane
Column chromatography is carried out for eluant, yellow solid is obtained for intermediate compound (Y4).
(5) with polymerized monomer (M1) is obtained after N- bromo-succinimides (NBS) bromination, its step is intermediate compound (Y4)：
Add 1-10mmol intermediate compounds 4,20-200mL chloroform in the good there-necked flask of clean dry successively so as to fully molten
Solution, then moves on to condition of ice bath stirring 10-60min.1-20mmol NBS are slowly added into again, are added and are reacted at room temperature again below
6-24 hours, reactant mixture are extracted with dichloromethane, and organic faciess are dried with anhydrous magnesium sulfate after washing again, are filtered, will
Filtrate obtains crude product after being spin-dried for solvent, crude product carries out column chromatography purification by eluant of petroleum ether, obtains yellow solid and is
Monomer (M1).
10. conjugated polymer according to claim 5, the preparation method of wherein monomer (M2) is：By compound (D6)-
78 DEG C are reacted with n-BuLi, then can be based on the monomer (M2) of (D6) again with trimethyltin chloride reaction.
11. conjugated polymers according to claim 7, the preparation method of wherein monomer (M3) is：Tied with electron deficiency conjugation
The dibromo compound of structure unit A is with duplex pinacol borate with double (diphenylphosphine) the ferrocene palladium chlorides of 1,1- as catalysis
Synthesize under conditions of agent.
Conjugated polymer shown in formula (I) is applied to system by a kind of 12. applications of the conjugated polymer containing benzo [c] cinnolines
Standby forward direction OPVs devices and reverse OPVs devices, wherein anode modification layer are PEDOT：PSS or MoO3, photoactive layer is polymer
(PZL-D or PZL-A)/PCBM or polymer (PZL-D or PZL-A)/non-fullerene electron acceptor material；Cathodic modification layer is
LiF, PFN, calcium etc.；Metal is aluminum or silver.
The application of 13. conjugated polymers according to claim 12, wherein preparing concretely comprising the following steps for positive OPVs devices：
The spin coating PEDOT/PSS solution (2000rpm, time are 30s) on ITO (tin indium oxide) electro-conductive glass of wash clean, then will
Which is placed in baking oven and toasts 10-30 minutes at a temperature of 150 DEG C (or the MoO that one layer of 10-30nm of evaporation is thick3), then will be poly-
The mixed solution spin coating of compound (PZL-D or PZL-A) and fullerene derivate thereon as photoactive layer, or by polymer
The solution spin coating of (PZL-D or PZL-A) and non-fullerene electron acceptor material is thereon as photoactive layer, the rotation of mixed solution
Painting speed is 600-4000rpm, then in the PFN of one layer of 2-15nm of photoactive layer spin coating, or the LiF of evaporation 0.2-0.8nm, or
The calcium of person 5-30nm, is then deposited with the metallic aluminium or silver of 50-150nm again, so as to prepare positive OPVs devices.
The application of 14. conjugated polymers according to claim 12, wherein preparing concretely comprising the following steps for reverse OPVs devices：
The PFN of one layer of 2-15nm of spin coating on ITO (tin indium oxide) electro-conductive glass of wash clean, then by polymer (PZL-D or PZL-
A) with the mixed solution spin coating of fullerene derivate thereon as photoactive layer, or by polymer (PZL-D or PZL-A) with
Thereon as photoactive layer, the spin coating speed of mixed solution is 600- for the solution spin coating of non-fullerene electron acceptor material
4000rpm, then the MoO of one layer of 5-20nm is deposited with photoactive layer3, the metallic aluminium or silver of 50-150nm are finally deposited with, so as to make
It is standby to obtain reverse OPVs devices.
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| CN108084408A (en) * | 2017-12-13 | 2018-05-29 | 湘潭大学 | A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide and preparation method thereof |
| CN111712928A (en) * | 2017-11-06 | 2020-09-25 | 密西根大学董事会 | Organic photovoltaic cell and non-fullerene receptor thereof |
| WO2021215632A1 (en) * | 2020-04-24 | 2021-10-28 | 부경대학교 산학협력단 | Polymer solar cell having cathode buffer layer including acid derivative-added conjugate polymer electrolyte |
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| JP2002284862A (en) * | 2001-03-23 | 2002-10-03 | Tdk Corp | Polymer compound and producing method and using method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111712928A (en) * | 2017-11-06 | 2020-09-25 | 密西根大学董事会 | Organic photovoltaic cell and non-fullerene receptor thereof |
| CN111712928B (en) * | 2017-11-06 | 2023-12-12 | 密西根大学董事会 | Organic photovoltaic cells and non-fullerene acceptors thereof |
| CN108084408A (en) * | 2017-12-13 | 2018-05-29 | 湘潭大学 | A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide and preparation method thereof |
| WO2021215632A1 (en) * | 2020-04-24 | 2021-10-28 | 부경대학교 산학협력단 | Polymer solar cell having cathode buffer layer including acid derivative-added conjugate polymer electrolyte |
| US12108654B2 (en) | 2020-04-24 | 2024-10-01 | Pukyong National University Industry-University Cooperation Foundation | Polymer solar cell having cathode buffer layer including acid derivative-added conjugate polymer electrolyte |
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Application publication date: 20170426 Assignee: HUNAN CHANGLI RAIL TRANSPORTATION EQUIPMENT Co.,Ltd. Assignor: XIANGTAN University Contract record no.: X2023980033020 Denomination of invention: A conjugated polymer containing benzo [c] miso line and its synthesis method and application Granted publication date: 20200505 License type: Common License Record date: 20230301 |