CN106588869B - Dialkyl group replaces naphtho- sulphur dibenzofuran monomer and preparation method thereof and replaces polymer and its application of naphtho- sulphur dibenzofuran unit containing dialkyl group - Google Patents
Dialkyl group replaces naphtho- sulphur dibenzofuran monomer and preparation method thereof and replaces polymer and its application of naphtho- sulphur dibenzofuran unit containing dialkyl group Download PDFInfo
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- CN106588869B CN106588869B CN201611009969.0A CN201611009969A CN106588869B CN 106588869 B CN106588869 B CN 106588869B CN 201611009969 A CN201611009969 A CN 201611009969A CN 106588869 B CN106588869 B CN 106588869B
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- China
- Prior art keywords
- dialkyl group
- thiophene
- naphtho
- monomer
- dibenzo
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 239000000178 monomer Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 230000005669 field effect Effects 0.000 claims abstract description 5
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 50
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- 229930192474 thiophene Natural products 0.000 claims description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
- 241000790917 Dioxys <bee> Species 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005893 bromination reaction Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 230000031709 bromination Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 4
- -1 boron Alkane Chemical class 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- VUVIRKAVBZITDO-UHFFFAOYSA-N 1-bromonaphthalene-2-carboxylic acid Chemical compound C1=CC=CC2=C(Br)C(C(=O)O)=CC=C21 VUVIRKAVBZITDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-M 2-naphthoate Chemical compound C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-M 0.000 claims 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims 1
- 238000006069 Suzuki reaction reaction Methods 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000010129 solution processing Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000000921 elemental analysis Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 229920000547 conjugated polymer Polymers 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- DJBMGTRWUAMBFN-UHFFFAOYSA-N 1-bromo-9-octylcarbazole Chemical compound BrC1=CC=CC=2C3=CC=CC=C3N(C12)CCCCCCCC DJBMGTRWUAMBFN-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 150000002220 fluorenes Chemical class 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
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UOPGXWZUDYOQEJ-UHFFFAOYSA-N 1-bromo-9,9-dioctylfluorene Chemical compound BrC1=CC=CC=2C3=CC=CC=C3C(C1=2)(CCCCCCCC)CCCCCCCC UOPGXWZUDYOQEJ-UHFFFAOYSA-N 0.000 description 3
- QGOOVNNHYVSYGR-UHFFFAOYSA-N BrC=1C(=C(C=CC1)OCCCCCCCC)OCCCCCCCC Chemical compound BrC=1C(=C(C=CC1)OCCCCCCCC)OCCCCCCCC QGOOVNNHYVSYGR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- FNLUIKNPCILERZ-UHFFFAOYSA-N 1,2-dioctoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1OCCCCCCCC FNLUIKNPCILERZ-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 2
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-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
- 238000003811 acetone extraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 229930000755 gossypol Natural products 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical class C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 description 1
- MFYGWCVLNPQWRR-UHFFFAOYSA-N 3,6-dibromo-9-octylcarbazole Chemical class BrC1=CC=C2N(CCCCCCCC)C3=CC=C(Br)C=C3C2=C1 MFYGWCVLNPQWRR-UHFFFAOYSA-N 0.000 description 1
- KVBLIDZBPXBVBU-UHFFFAOYSA-N 3-bromopyrrolidine-2,5-dione sulfuric acid Chemical compound BrC1C(=O)NC(C1)=O.S(O)(O)(=O)=O KVBLIDZBPXBVBU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- 230000005526 G1 to G0 transition Effects 0.000 description 1
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- 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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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
Replace naphtho- sulphur dibenzofuran monomer and preparation method thereof the invention discloses dialkyl group and replaces polymer and its application of naphtho- sulphur dibenzofuran unit containing dialkyl group.Dialkyl group replaces in naphtho- sulphur dibenzofuran monomer, there are strong electrophilic unit-SO2-, is conducive to mention high molecular electron affinity;The introducing of the condensed cyclic structure and alkyl of Asymmetrical substitute while advantageously reducing the electron affinity of monomer, substantially improves the dissolubility of monomer in organic solvent.Dialkyl group replaces naphtho- sulphur dibenzofuran monomer to pass through Suzuki, Stille or Yamamoto polymerization reaction obtains the homopolymer or copolymer for replacing naphtho- sulphur dibenzofuran unit containing dialkyl group, obtained polymer has good dissolubility in organic solvent, it is suitble to solution processing, has a wide range of applications in preparing electroluminescent device, organic photovoltaic cell and organic field effect tube.
Description
Technical field
The present invention relates to organic photoelectrical material technical fields, and in particular to dialkyl group replaces naphtho- sulphur dibenzofuran monomer and its system
Preparation Method and polymer and its application for replacing naphtho- sulphur dibenzofuran unit containing dialkyl group.
Background technique
In the past twenty years, organic electronic and photoelectronic industry, including organic/polymer LED, it is organic
The fields such as field effect transistor, organic photovoltaic cell, nonlinear optics, biosensor and laser have all obtained swift and violent development
And gradually move towards industrialization.Organic electronic product has many advantages, such as cheap, and body is light to be taken, and it is latent to make it have very big market
Power.Therefore, there is the organic electronic product of market attractiveness to have attracted numerous in the world research institution and Research Team for exploitation
Concern and investment.And among these, developing the link that new and effective stable material undoubtedly becomes crucial.
S, S- dioxo-dibenzothiophene (SO) are the short of electricity subelement having many advantages, such as, strong electron-withdrawing group group-
SO2The electron affinity of molecule, higher electron mobility can be improved, and S atom has reached highest price and is good for state, tool
There is inoxidizability;-SO2Introducing will not substantially reduce the fluorescence quantum efficiency etc. of material, the especially-S containing 3,7- substitution,
The polymer of S- dioxo-dibenzothiophene unit shows superior electroluminescent properties, and luminescent device is in very big electric current
It is demonstrated by superior spectrum stability in density and heat-treatment temperature range, and people is caused widely to pay close attention to.But due to S,
The dissolubility of S- dioxo-dibenzothiophene unit is poor, it is difficult to obtain high S, the polymerization of S- dioxo-dibenzothiophene unit content
Object, and since the flatness of 3,7- substitution-S, S- dioxo-dibenzothiophene unit is preferable, obtained polymer send out coloured light sky blue,
It is insufficient as being shown slightly for full-color EL display material.The angle chemically synthesized, S, S- dioxo-dibenzothiophene is unlike fluorenes or click
Azoles is easy to be modified at C-9 or N-9 like that, thus greatly limits its application in field of photovoltaic materials.Cause
This develops new method to be modified S, and S- dioxo-dibenzothiophene unit just seems very necessary.
The present invention develops novel dialkyl group and replaces naphtho- sulphur dibenzofuran monomer and preparation method thereof and polymer and its application.
Polymer containing the monomer has good dissolubility, is suitable for solution processing;Its luminescent device not only efficient stable, but also for more
Blue saturation blue light, can fully meet the requirement that full color flat panel is shown.Replace S, S- dioxy-dibenzo thiophene additionally, due to dialkyl group
The space steric effect of pheno unit replaces the copolymer of naphtho- sulphur dibenzofuran unit and the triplet of homopolymer based on dialkyl group
And electron mobility will all obviously increase, as phosphorescent light body material and electron acceptor material in white-light illuminating and solar cell
Aspect will have very big application potential.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which providing dialkyl group replaces naphtho- sulphur dibenzofuran monomer and its system
Preparation Method.The monomer synthesizing and purifying be easy, low in raw material price, be conducive to mass production;Meanwhile asymmetric condensed cyclic structure and length
The introducing of alkyl chain reduce monomer coplanarity, improve dissolubility, in terms of play critical effect.
The object of the invention is also to provide the conjugation for the structural unit for replacing naphtho- sulphur dibenzofuran monomer containing the dialkyl group
Polymer.
The object of the invention is also to provide replace the conjugated polymer of naphtho- sulphur dibenzofuran unit to exist containing the dialkyl group
Prepare the application in electroluminescent device, organic photovoltaic cell and organic field effect tube.
Dialkyl group replaces naphtho- sulphur dibenzofuran monomer, has following chemical structural formula:
In formula, X is Br or I atom;R is the straight chain or branched alkyl of carbon atom number 1-30.
The dialkyl group replaces the preparation method of naphtho- sulphur dibenzofuran monomer, includes the following steps:
(1) under chloroform environment, with bromine by dibenzo [b, d] thiophene bromination at 2- bromine dibenzo [b, d] thiophene;
(2) 2- bromine dibenzo [b, d] thiophene is dissolved in THF, at -70~-80 DEG C, dropwise addition butyl lithium, reaction 2~
3 hours;Then it maintains the temperature under the conditions of -70~-80 DEG C, 2- isopropoxy -4,4,5,5- tetramethyls -1,3,2- dioxy is added
Then miscellaneous borine is warmed to room temperature reaction 18~24 hours after the reaction was continued 1~2 hour;2- (dibenzo [b, d] thiophene-is made
2- yl) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate;
(3) in toluene solvant, with 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- dioxy
Miscellaneous borine and the bromo- 2- naphthoate of methyl 1- are reaction raw materials, and under alkaline environment, closing palladium with four (triphenylphosphines) is catalysis
Methyl 1- (two is made by Suzuki, Stille or Yamamoto polymerization reaction 12~18 hours at 120~150 DEG C in agent
Benzo [b, d] thiophene -2- base) -2- naphthoate;
(4) methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate is dissolved in THF, alkyl bromination is added dropwise
Magnesium, 100~120 DEG C back flow reaction 12~18 hours, be made 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol;
(5) 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol is dissolved in methylene chloride, concentration is added dropwise
For 46.5%~48% Eorontrifluoride etherate solution, 0~5 DEG C progress ring closure reaction 1~2 hour, 14,14- dioxane is made
Base -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene;
(6) be oxidant with hydrogen peroxide in acetic acid solvent, by 14,14- dialkyl group -14H- benzo [b] benzo [5,
6] fluorenes [1,2-d] thiophene is oxidized to monomer 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- bis-
Oxygen;
(7) 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy is used in sulfuric acid
Bromo-succinimide bromination obtains the dialkyl group and replaces naphtho- sulphur dibenzofuran monomer.
Further, in step (1), the brominated temperature is no more than 5 DEG C, and the brominated time is 12~18 hours.
Further, in step (2), the molar ratio of 2- bromine dibenzo [b, the d] thiophene and butyl lithium is 1:1.5~1:
2。
Further, in step (2), 2- bromine dibenzo [b, the d] thiophene and 2- isopropoxy -4,4,5,5- tetramethyls
The mass ratio of base -1,3,2- dioxaborinate is 1:0.9~1:1.5.
Further, in step (3), the 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2-
The molar ratio of dioxaborinate and the bromo- 2- naphthoate of methyl 1- is 1:1.2~1:1.5.
Further, in step (4), methyl 1- (dibenzo [b, d] thiophene -2- the base) -2- naphthoate and alkyl
The molar ratio of magnesium bromide is 1:3~1:5.
Further, in step (5), 2- (1- (dibenzo [b, the d] thiophene -2- base) naphthalane -2- base) isopropanol with
The solid-liquid ratio of Eorontrifluoride etherate solution is 4:1~4.5:1g/mL.
Further, in step (6), the oxidation reaction is reacted 2~5 hours at 100~120 DEG C.
Further, in step (7), 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1, the 2-d] thiophene
The molar ratio of 9,9- dioxy and bromo-succinimide is 1:2~1:2.5.
Further, in step (7), the bromination reaction is reacted 18~24 hours at 0~5 DEG C.
Replace the polymer of the structural unit of naphtho- sulphur dibenzofuran monomer containing dialkyl group, there is following chemical structural formula:
In formula: R is the straight chain or branched alkyl of carbon atom number 1-30, and x, y are molar fraction, 0 < x≤1, x+y=1,
Polymerization degree n=1~300;
Wherein: one of Ar has the following structure:
In formula, R1For the straight chain or branched alkyl of carbon atom number 1-30.
It is described containing dialkyl group replace naphtho- sulphur dibenzofuran monomer structural unit polymer prepare electroluminescent device,
Application in organic photovoltaic cell and organic field effect tube.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) monomer of the present invention increases asymmetrical condensed cyclic structure simultaneously on the basis of S, S- dioxo-dibenzothiophene unit
Long alkyl chain is introduced, while reducing the flatness of monomer, increases the solvent borne of monomer and its polymer, is improved prepared
The luminescent saturation degree and molecular weight of polymer reduce polymer molecule chain end group defect, improve the filming performance of polymer.
(2) the present invention provides the synthetic route that effective dialkyl group replaces naphtho- sulphur dibenzofuran monomer, synthesizing and purifying is easy,
Low in raw material price is conducive to scale preparation production.
(3) the present invention is based on the conjugated polymer dissolubilities in organic solvent that dialkyl group replaces naphtho- sulphur dibenzofuran monomer
It is good, device can be prepared with Solution processing techniques;Simultaneously as its conduct of the good electron deficient performance guarantee of polymer obtained
The balance of electrons and holes injection transmission when luminescent layer, to significantly improve the luminous efficiency of device.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism figure that dialkyl group replaces naphtho- sulphur dibenzofuran monomer;
Fig. 2 is the thermogravimetric curve of polymer P 1, P2 and P3;
Fig. 3 is the electroluminescent spectrum of polymer P 1;
Fig. 4 is the electro-chemical test curve of polymer P 2.
Specific embodiment
Following embodiment is only used for that the present invention is further explained, without limiting the present invention.
Embodiment 1
The preparation of 2,7- dibromo fluorenes
In the there-necked flask of 1000mL, fluorenes (60g, 301mmol), iron powder (0.84g, 15mmol) and chloroform is added
(400mL), ice bath (5 DEG C) are protected from light down, and the mixed liquor of bromine (35mL, 753mmol) and 115mL chloroform is slowly dropped to reaction
It in solution, finishes, is reacted 12 hours in room temperature strong stirring.Bisulfite saturated aqueous solution of sodium 200mL is added into reaction flask
Quenching reaction.Reaction mixture is filtered, filter residue is successively with saturation aqueous solution of sodium bisulfite, water and ethanol washing three
It is secondary, after filter residue and drying, use CHCl3Recrystallization carries out purification process, obtains white crystal 77.8g, yield: 80%.1H NMR
(300MHz,CDCl3) (ppm): 7.54 (d, 2H), 7.44 (d, 2H), 7.31 (d, 2H), 3.86 (m, 2H).13C NMR(75MHz,
CDCl3) (ppm): 152.91,144.49,134.89,128.91,121.31,119.53,76.54.Elemental analysis result:
C13H8Br2, theoretical value: C, 48.14%;H, 2.46%.Actual measured value: C, 48.21%;H, 2.63%.
Embodiment 2
The preparation of the bromo- 9,9- dioctyl fluorene (M-1) of 2,7- bis-
Under argon gas protection, in 500mL three-necked flask, 2,7- dibromo fluorenes (32.4g, 100mmol) is added and dimethyl is sub-
Sulfone (250mL) under strong stirring, is added tetrabutylammonium bromide (1.61g, 5mmol), be then slowly added dropwise sodium hydroxide (40g,
1000mmol) 50wt% aqueous solution finishes, and reacts 2 hours, property injection 1- bromooctane (57.9g, 300mmol) again.Continue
After reaction 10 hours, stop reaction, reaction solution be poured into water, aqueous hydrochloric acid solution is added and is neutralized, is extracted with dichloromethane,
It is washed 7 times with saturated common salt, it is dry, after being spin-dried for solvent, crude product is purified with column chromatography method, uses silica gel as fixation
Phase, uses petroleum ether as mobile phase, obtains white solid 43.8g after purification, yield: 80%.1H NMR(300MHz,CDCl3)
(ppm): 7.53 (d, 2H), 7.46 (d, 2H), 7.41 (d, 2H), 1.94 (m, 4H), 1.20-1.04 (m, 20H), 0.84 (t,
6H), 0.53 (m, 4H).13C NMR(75MHz,CDCl3) (ppm): 152.96,139.46,130.54,126.56,121.87,
121.54,56.11,40.52,32.17,30.26,29.54,24.04,23.01,14.51.Elemental analysis result: C29H40Br2,
Theoretical value: C, 63.51%;H, 7.31%.Actual measured value: C, 63.53%;H, 7.42%.
Embodiment 3
The preparation of bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- the base) -9,9- dioctyl fluorenes (M-2) of 2,7-
Under argon gas protection, in 500mL long there-necked flask, bromo- 9, the 9- dioctyl fluorene (21.9g, 40mmol) of 2,7- bis- is added
With anhydrous tetrahydro furan 250mL, reaction solution is cooled to -78 DEG C with liquid nitrogen, the hexane solution into n-BuLi is slowly added dropwise
(48mL, 2.5M, 120mmol) is kept after stirring 2 hours at -78 DEG C, disposable to inject 2- isopropyl -4,4,5,5- tetramethyls -
1,3,2- dioxaborinate (26g, 140mmol), allows it to be warmed to room temperature naturally, the reaction was continued 20h.Aqueous ammonium chloride solution is added to quench
It goes out reaction, rotary evaporation falls most of solvent, and reaction mixture is poured into water, and is extracted with dichloromethane, and washes 5 times, separation
Organic phase dries, filters after being spin-dried for solvent, is purified with column chromatography method to crude product, uses silica gel as stationary phase, use stone
Oily ether/methylene chloride obtains white solid 43.8g, yield: 80% as mobile phase after purification.1H NMR(300MHz,CDCl3)
(ppm): 7.80 (d, 2H), 7.73 (s, 2H), 7.72 (d, 2H), 1.98 (m, 4H), 1.38 (s, 24H), 1.21-1.01 (m,
20H), 0.80 (t, 6H), 0.55 (m, 4H).13C NMR (75MHz, CDCl3) (ppm): 150.85,144.31,134.03,
129.28,119.76,84.10,55.56,40.48,32.17,30.32,29.57,25.32,23.97,22.98,14.47.Member
Element analysis result: C41H64O4B2, theoretical value: C, 76.73%;H, 10.05%.Actual measured value: C, 76.43%;H, 9.91%.
Embodiment 4
The preparation of 3,6- dibromo carbazole
Carbazole (24.7g, 0.1mol) is added in 500mL three-necked flask, dimethylformamide 200mL, stirring to dissolution,
NBS (49.84g, 0.28mol) 120mL DMF dissolves, and NBS solution is slowly added dropwise to 0 DEG C in ice bath, and reaction is protected from light, and is dripped
Bi Hou allows temperature to rise to room temperature automatically, reacts 6 hours.Reaction solution is added drop-wise in water and is precipitated, suction filtration obtains crude product
Afterwards, object will be filtered to be recrystallized with dehydrated alcohol, dries, obtains white needle-like crystals, yield: 85%.1H NMR(300MHz,CDCl3)
δ(ppm):8.11(d,2H),8.03(s,1H),7.51(m,2H),7.29(t,2H).Elemental analysis result (%): C12H7NBr2,
Calculated value: C, 44.31%;H, 2.15%;N, 4.31%;Test value: C, 44.28;H,2.20;N, 4.26%.
Embodiment 5
The preparation of the bromo- N- octylcarbazol (M-3) of 3,6- bis-
3,6- dibromo carbazole (16.25g, 0.05mol), toluene (100mL), the tetrabutyl are added in 250mL three-necked flask
50wt%KOH (11mL) solution is slowly added dropwise in ammonium bromide (0.8g, 3.5mmol), stirring and dissolving, after again plus n-C8H17Br
(19.3g, 0.1mol) adds water to terminate reaction after heating reaction for 24 hours, and washing separation goes out organic phase, water phase CH2Cl2After extraction
Washing twice, merges organic phase, with anhydrous MgSO4It is dry.Vacuum distillation obtains light yellow solid after removing solvent, uses petroleum ether
It is recrystallized to give white powdery solids.Yield: 95%.1H NMR(300MHz,CDCl3)δ(ppm):8.18(s,2H),7.56
(d,2H),7.24(d,2H),4.21(t,2H),1.83(t,2H)1.33-1.24(m,10H),0.85(t,3H).Elemental analysis knot
Fruit (%): C20H23Br2N, calculated value: C, 54.94;H,5.30;N,3.20;Test value: C, 54.88;H,5.20;N, 3.26%.
Embodiment 6
The preparation of 3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate-diyl)-N- octylcarbazol (M-4)
The ether 250mL that the bromo- N- octylcarbazol (13.11g, 30mmol) of 3,6- bis- is added in three-necked flask, newly steams, is stirred
It mixes and is completely dissolved to clear liquid.Reaction solution is cooled to -78 DEG C, n-BuLi (2.5M, 75mmol) is slowly added dropwise,
Continue stirring 2 hours at -78 DEG C, reaction solution is white paste at this time.Then cold-trap is removed to be slowly increased to react at room temperature by it,
Reaction solution is faint yellow clear liquid.Reaction be cooled to -78 DEG C again, be then added at one time 2- isopropoxy-(4,4,5,
5- tetramethyl) -1,3,2- ethylenedioxy borates (37mL, 180mmol), are stirred 2 hours, then temperature is risen to room at -78 DEG C
Reaction was completed after 24 hours for temperature reaction.It is extracted with ether, it is saturated common salt water washing 4 times, dry with anhydrous magnesium sulfate.After filtering,
Solvent is distilled off, product petroleum ether/ethyl acetate (10:1) is eluant, eluent column Chromatographic purification, white crystal is obtained, yield:
45%.1H NMR(300MHz,CDCl3)δ(ppm):8.67(s,2H),7.91(d,2H),7.40(d,2H),4.31(t,2H),
1.88 (t, 2H), 1.31-0.96 (m, 34H), 0.85 (t, 3H).Elemental analysis result (%): C32H47B2NO4, calculated value: C,
72.33;H,8.92;N,2.64;Test value: C, 72.51;H,9.02;N,2.73.
Embodiment 7
The preparation of bis- octyloxy benzene of 1,4-
Under argon gas protection, hydroquinone (2.2g, 20mmol) is added in 250mL three-necked flask, is saturated KOH aqueous solution
5mL, ethyl alcohol 100mL, then stirring is warming up to reflux to dissolving, and reacts 1 hour, dropwise addition bromooctane under reflux state (9.65g,
50mmol), after being added dropwise, continue back flow reaction 8 hours, be cooled to room temperature, there are a large amount of flakey substances to be precipitated in bottle, take out
Pure products can be obtained with ethyl alcohol recrystallization in filter, obtained crude product.1H NMR(300MHz,CDCl3)δ(ppm):7.03(d,4H),
4.08(t,4H),1.79-1.74(m,4H),1.46(m,4H),1.32-1.25(m,16H),0.92-0.88(m,6H).Element point
Analyse result (%): C22H38O2, calculated value: C, 78.99;H,11.45;O,9.56;Test value: C, 77.88;H,11.39;O,
9.41。
Embodiment 8
The synthesis of the bromo- bis- octyloxy benzene (M-5) of 2,5- of 1,4- bis-
It takes-two octyloxy benzene (3.35g, 0.01mol) of Isosorbide-5-Nitrae to be dissolved in 100mL carbon tetrachloride, is quickly stirred to react, keeps away
When ice bath is cooled to 5 DEG C, bromine (4g, 0.025mol) is slowly added dropwise in light, is stirred to react overnight, is then poured into reaction solution full
And NaHSO3It in solution, is extracted with ethyl acetate, washes, anhydrous magnesium sulfate is dry, steams solvent, and crude product is with petroleum ether/bis-
Chloromethanes (10:1) is eluant, eluent column Chromatographic purification, obtains white needle-like crystals with Gossypol recrystallized from chloroform.1H NMR(300MHz,
CDCl3)δ(ppm):7.20(s,2H),4.08(t,4H),1.79-1.74(m,4H),1.46(m,4H),1.32-1.25(m,
16H),0.92-0.88(m,6H).Elemental analysis result (%): C22H36Br2O2, calculated value: C, 53.67;H,7.37;O,6.50;
Test value: C, 53.52;H,7.29;O,6.38.
Embodiment 9
2,2 '-((the octyloxy) -1,4- of 2,5- bis- phenyl) two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate) (M-
6) preparation
The bromo- bis- octyloxy benzene (7.48g, 0.015mol) of 2,5- of 1,4- bis- is taken to be dissolved in the ether that 300mL re-distillation is crossed
In, be cooled to -78 DEG C under nitrogen atmosphere, be slowly added dropwise n-BuLi (hexane solution of 15.1mL, 2.5mol/L,
0.038mol), addition 2- isopropyl -4,4 after -78 DEG C of heat preservation 2h, 5,5- tetramethyls -1,3,2- dioxaborinate (7.75mL,
0.0375mol), 48h is reacted at room temperature.After reaction with ether and distilled water extraction, washing, anhydrous magnesium sulfate drying.It steams
Solvent out, n-hexane are recrystallized to give 3.1g white needle-like crystals, yield: 35.1%.1H NMR(300MHz,CDCl3)δ
(ppm):7.10(s,2H),3.97-3.93(t,4H),1.79-1.74(m,4H),1.57-1.50(m,4H),1.37-1.30(m,
40H),0.92-0.88(m,6H)。13C NMR(75MHz,CDCl3)δ(ppm):157.70,119.96,83.43,69.80,
31.88,29.68,29.51,29.35,25.08,24.85,22.67,14.07.Elemental analysis result (%): C34H60B2O6, meter
Calculation value: C, 69.63;H,10.31;O,16.37;Test value: C, 69.55;H,10.19;O,16.23.
Embodiment 10
The preparation of 2- bromine dibenzo [b, d] thiophene
In 500mL there-necked flask, dibenzo [b, d] thiophene (22g, 0.12mol), iron powder (0.33g, 6mmol), three is added
Chloromethanes 200mL.Ice-water bath is cooling, and bromine (6.2mL, 0.12mol) syringe is injected flask.When dropwise addition bottle in temperature not
More than 5 DEG C.Reaction 12 hours, stops reaction, and filtering, Gossypol recrystallized from chloroform obtain white solid 19.5g, yield: 62%.1H NMR
(300MHz,CDCl3) δ (ppm): 8.46 (d, 1H), 7.94 (d, 1H), 7.92 (d, 1H), 7.86 (d, 1H), 7.56 (t, 1H),
7.49(t,1H),744(d,1H).Elemental analysis result (%): C12H7BrS, calculated value: C, 54.77;H,2.68;S,12.18;
Test value: C, 54.68;H,2.55;S,12.04.
Embodiment 11
The preparation of 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate
2- bromine dibenzo [b, d] thiophene (12.0g, 45.6mmol) is dissolved in the anhydrous THF of purification (200mL) ,-
The n-BuLi (57mL, 91.2mmol) of 1.6mol/L is gradually added dropwise at 78 DEG C, reacts 2 hours, 2- isopropoxy-is then added dropwise
4,4,5,5- tetramethyls -1,3,2- dioxaborinate 11.03g, the reaction was continued at -78 DEG C 1 hour, is warming up to room temperature reaction 24
Hour.Reaction mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds anhydrous slufuric acid
Magnesium is dry.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selects petroleum ether/dichloro with silica gel column chromatography purification
Methane=5/1, v/v), yellow oily liquid 8.2g is obtained, yield: 58%.1H NMR(300MHz,CDCl3)δ(ppm):8.46
(d,1H),7.96(d,1H),7.94(d,1H),7.92(d,1H),7.56(t,1H),7.49(t,1H),7.44(t,1H),1.28
(t,12H).Elemental analysis result (%): C18H19BO2S, calculated value: C, 69.69;H,6.17;S,10.33;Test value: C,
69.57;H,6.02;S,10.14.
Embodiment 12
The preparation of methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate
In 500mL three-necked flask, 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- bis- is added
Oxa- borine (7.7g, 24.82mmol), 200mL toluene stirring and dissolving are then separately added into methyl 1- bromonaphthalene formic acid esters
(8.55g, 32.3mmol), Na2CO3(13.15g, 124.11mmol), four butyl bromation amine (4mg, 12.4umol), organic base
(10mL), deionized water 30mL, catalyst four (triphenylphosphine) close palladium (1.43g, 1.24mmol), are heated to 150 DEG C, reaction
12h.After reaction solution is concentrated, with silica gel column chromatography (eluant, eluent selects petroleum ether, methylene chloride=5/1, v/v), yellow is obtained
Grease 5.5g, yield: 60%.1H NMR(300MHz,CDCl3)δ(ppm):8.90(d,1H),8.45(d,1H),8.17(t,
1H),8.12(d,3H),7.99(d,1H),7.93(d,1H),7.82(s,1H),7.56(t,1H),7.51(t,1H),7.49(t,
1H),7.32(t,1H),3.90(t,3H).Elemental analysis result (%): C24H16O2S, calculated value: C, 78.24;H,4.38;S,
8.70;Test value: C, 78.11;H,4.27;S,8.55.
Embodiment 13
The preparation of 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane -2- base) isopropanol
Methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate (5.0g, 13.6mmol) is dissolved in purification
In anhydrous THF (150mL), 1.6mol/L methyl-magnesium-bromide (25.4g, 40.7mmol) is added dropwise dropwise, is warming up to 100 DEG C and heats back
Stream reacts 12h.It is cooled to room temperature, reaction mixture is poured into water, be extracted with ethyl acetate, organic layer saline solution is complete
It is dry with anhydrous magnesium sulfate after washing.After solution concentration, with silica gel column chromatography, (eluant, eluent selects petroleum ether, methylene chloride=1/
1, v/v) white solid 2.5g, is obtained, yield: 50%.1H NMR(300MHz,CDCl3)δ(ppm):8.92(d,1H),8.45
(d,1H),8.12(t,3H),7.98(d,2H),7.93(d,1H),7.56(t,1H),7.48(d,2H),7.34(t,1H),7.09
(t,1H),5.52(s,1H),1.41(t,6H).Elemental analysis result (%): C25H20OS, calculated value: C, 81.49;H,5.47;
S,8.70;Test value: C, 81.32;H,5.31;S,8.55.
Embodiment 14
The preparation of 14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene
2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane -2- base) isopropanol (2.3g, 6.24mmol) is dissolved in dichloro
In methane 150mL, it is added 0.5mL Eorontrifluoride etherate solution (concentration 46.5%), 3 DEG C of reaction 1h.After solution concentration, use
Silica gel column chromatography method purification, obtains white solid.Twice with ethyl alcohol recrystallization, white crystal 1.8g is filtered to obtain, yield:
82.6%.1H NMR(300MHz,CDCl3)δ(ppm):8.85(d,1H),8.45(d,1H),8.08(t,1H),7.93(d,1H),
7.91(t,2H),7.88(d,1H),7.56(t,1H),7.49(t,1H),7.40(t,1H),7.29(t,1H),7.09(d,1H),
1.75(t,6H).Elemental analysis result (%): C25H18S, calculated value: C, 85.68;H,5.18;S,9.15;Test value: C,
85.53;H,5.10;S,9.04.
Embodiment 15
The preparation of 14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy
In 250mL three-necked flask, 14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene is added
(10.5g, 30mmol) and acetic acid (100mL), is added with stirring 30mL H2O2, it is small that reaction is heated to the lower reaction 2 of 100 DEG C of reflux
When, reaction terminates, and solvent is removed in rotation, and crude product with methanol is recrystallized, and obtains white solid, yield: 85% after purification.1H NMR
(300MHz,CDCl3)δ(ppm):8.87(dd,2H),8.56(d,1H),7.98(m,2H),7.91(dd,2H),7.68(m,
2H),7.52(m,3H),1.96(t,6H).Elemental analysis result (%): C25H18O2S, calculated value: C, 78.51;H,4.74;S,
8.38;Test value: C, 78.36;H,4.49;S,8.12.
Embodiment 16
Dialkyl group replaces the preparation of naphtho- sulphur dibenzofuran (M-7)
In 500mL single-necked flask, 14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene is added
9,9- dioxies (15.3g, 40mmol) and sulfuric acid (200mL) are protected from light and NBS (17.8g, 100mmol) are added, reacts at room temperature.With
The test of silica gel plate contact plate stops reaction, reaction solution is added slowly to sulfurous until most of raw material is converted into disubstituted product
In the ice water solution of sour hydrogen sodium, there are a large amount of solids to be precipitated, filters, successively washed with sodium bicarbonate aqueous solution, water and methanol.With stone
Oily ether/methylene chloride is that eluant, eluent carries out column chromatography, obtains white solid.Yield: 70%.1H NMR(300MHz,CDCl3)δ
(ppm):8.87(dd,2H),8.56(d,1H),7.91(dd,2H),7.68(m,2H),7.52(m,3H),1.96(t,6H).Member
Element analysis result (%): C25H16Br2O2S, calculated value: C, 55.58;H,2.99;S,5.93;Test value: C, 55.39;H,2.84;
S,5.81。
Fig. 1 is that the dialkyl group of preparation replaces naphtho- sulphur dibenzofuran monomer1H NMR spectra, from fig. 1, it can be seen that having 10 on phenyl ring
In addition a H has 6 H, complies fully with the structure of molecule at δ 1.96ppm, illustrate that the white solid of synthesis is target molecule.
Embodiment 17
9,9- dioctyl substituted fluorene-co-14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,
The synthesis of 9- dioxy polymer (P1)
Under argon gas protection, 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- ethylenedioxy boron are added in the two-mouth bottle of 50mL
Acid esters-diyl) -9,9- bis- (octyl) fluorenes (M-2) (321.3mg, 0.5mmol), 2,7- bis- bromo- 9,9- bis- (octyl) fluorenes (M-1)
(268.4mg, 0.49mmol), dialkyl group replace naphtho- sulphur dibenzofuran (M-7) (5.40mg, 0.01mmol) and palladium acetate
(2.24mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), argon gas protection is lower to inject 12mL toluene, stirring half
After hour, when being heated to 80 DEG C of reflux, tetraethyl ammonium hydroxide (20wt%) aqueous solution (4mL) is injected, under an argon atmosphere instead
After answering 24 hours, phenyl boric acid (18.3mg, 0.15mmol) sealing end is added, bromobenzene (0.3mL, 3mmol) is added again in the reaction was continued 8h
Secondary sealing end stops reaction after 8h, is cooled to room temperature;Product is precipitated out in methyl alcohol, methanol and acetone respectively extract 48 respectively
Hour removes oligomer and catalyst;Then it is precipitated in methyl alcohol repeatedly after being dissolved in toluene;Using column chromatography method into one
Separating-purifying polymer is walked, faint yellow fibrous solids 298mg, yield: 85% are obtained after vacuum drying.
Fig. 2 gives the thermogravimetric curve of polymer P 1, and as can be seen from Figure 2, the thermal decomposition temperature of polymer P 1 is 412 DEG C,
Illustrate that the polymer has good hot property, this is extremely important for preparing for electroluminescent device.
Fig. 3 gives the electroluminescent light spectrogram of polymer P 1, from figure 3, it can be seen that due in polymer dialkyl group take
Low, the only 1mol% for the comparision contents of naphtho- sulphur dibenzofuran unit, so polymer mainly shows the electroluminescent light of polyfluorene
Spectrogram, maximum emission peak position is at 434nm.
Embodiment 18
3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate-diyl)-N- octylcarbazol-co-14,14- diformazan
The synthesis of base -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy polymer (P2)
Under argon gas protection, 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxa boron are added in the two-mouth bottle of 50mL
Alkane-diyl)-N- octylcarbazol (M-4) (265.7mg, 0.5mmol), 3,6- bis- bromo- N- octylcarbazols (M-3) (214.2mg,
0.49mmol), dialkyl group replace naphtho- sulphur dibenzofuran (M-7) (5.40mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg,
0.025mmol), argon gas protection is lower injects 8mL toluene, after stirring half an hour, when being heated to 82 DEG C of reflux, injects tetraethyl hydrogen-oxygen
Change ammonium (30wt%) aqueous solution (2mL), after reacting 36 hours under an argon atmosphere, is added phenyl boric acid (19.5mg, 0.16mmol)
Sealing end, the reaction was continued 10h are added bromobenzene (0.35mL, 3.5mmol) and block again, stop reaction after 10h, be cooled to room temperature;It will
Product is precipitated out in methyl alcohol, uses 48 hours removing oligomer of methanol and acetone extraction and catalyst respectively;Then in toluene
It is precipitated in methyl alcohol repeatedly after middle dissolution;Using the further separating-purifying polymer of column chromatography method, obtained after vacuum drying light
Yellow powdery solid 265mg, yield: 63%.
Fig. 2 gives the thermogravimetric curve of polymer P 2, and as can be seen from Figure 2, the thermal decomposition temperature of polymer P 2 is 410 DEG C,
Illustrate that the polymer has good hot property, this is extremely important for preparing for electroluminescent device.
Fig. 4 gives the electro-chemical test curve of polymer P 2, and as can be seen from Figure 4, the oxidizing potential of polymer P 2 is
1.24V。
Embodiment 19
2,5- bis- octyloxy benzene-co-14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9-
The synthesis of dioxy polymer (P3)
Under argon gas protection, be added 2,2 '-(2,5- bis- (octyloxies)-Isosorbide-5-Nitrae-phenyl) two in the two-mouth bottle of 50mL (4,4,
5,5- tetramethyls -1,3,2- dioxaborinate) (M-6) (293.2mg, 0.5mmol), bromo- 2,5-, the bis- octyloxy benzene (M- of Isosorbide-5-Nitrae-two
5) (241.2mg, 0.49mmol), dialkyl group replace naphtho- sulphur dibenzofuran (M-7) (5.40mg, 0.01mmol) and palladium acetate
(5.40mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), argon gas protection is lower to inject 12mL toluene, stirring half
After hour, when being heated to 85 DEG C of reflux, tetraethyl ammonium hydroxide (20wt%) aqueous solution (4mL) is injected, under an argon atmosphere instead
After answering 48 hours, phenyl boric acid (20.7mg, 0.17mmol) sealing end is added, the reaction was continued 12h, addition bromobenzene (0.4mL, 4mmol)
It blocks again, stops reaction after 12h, be cooled to room temperature;Product is precipitated out in methyl alcohol, uses methanol and acetone extraction respectively
48 hours removing oligomer and catalyst;Then it is precipitated in methyl alcohol repeatedly after being dissolved in toluene;Using column chromatography method into
One step separating-purifying polymer, obtains light green fibrous solids 280mg, yield: 64% after vacuum drying.
Fig. 2 gives the thermogravimetric curve of polymer P 3, and as can be seen from Figure 2, the thermal decomposition temperature of polymer P 3 is 411 DEG C,
Illustrate that the polymer has good hot property, this is extremely important for preparing for electroluminescent device.
The composition and performance of conjugated polymer P1~P3 of preparation is enumerated as shown in table 1.
The composition and performance of 1 conjugated polymer P1~P3 of table
As shown in Table 1, the molecular weight of the conjugated polymer prepared based on fluorenes and benzene is bigger, with carbazole for main system
The molecular weight of standby conjugated polymer is smaller, the main reason is that carbazole is lower compared with the activity of fluorenes and benzene;It is contracted by Suzuki
The poly- coefficient of dispersion for reacting all conjugated polymers being prepared is relatively narrow, and the coefficient of dispersion is between 1.9-2.2, all polymerizations
The photoluminescence quantum efficiencies of object are higher, and photoluminescence quantum efficiencies are between 59-70%.
The following are the preparations for replacing naphtho- sulphur dibenzofuran polymer light-emitting device based on the dialkyl group
Embodiment 20
Based on polymer 9,9- dioctyl substituted fluorene-co-14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,
2-d] thiophene 9,9- dioxy polymer (P1) electroluminescent device preparation
It is first successively to use acetone, washing on 15 Ω/ tin indium oxide (ITO) glass in the square resistance of well in advance
Agent, deionized water and isopropanol ultrasonic cleaning, plasma treatment 10 minutes;Spin coating is doped with polystyrolsulfon acid on ITO
Polyethoxy thiophene (PEDOT:PSS) film, with a thickness of 150nm.PEDOT:PSS film is 8 hours dry at 80 DEG C in vacuum drying oven;
The xylene solution (1wt%) of polymer P 1 is then spin-coated on to the surface of PEDOT:PSS film, with a thickness of 80nm;Finally sending out
The metal Al layer of a thin layer CsF (1.5nm) and 120nm thickness are successively deposited on photosphere.
Based on single layer device structure: ITO/PEDOT:PSS/emitter/CsF/Al, single layer device prepared by polymer P 1
Maximum lumen efficiency be 3.05cd/A, maximum external quantum efficiency is 3.57%, and due to single layer device structure, hole and electronics are passed
Defeated imbalance, exciton is not effectively used to shine, so performance is relatively low.
The work of further device optimization is also carrying out, in single layer device structure, since carrier transport is uneven,
Increase hole transmission layer or electron transfer layer in the device structure, while improving carrier transport balance, will can effectively swash
Son is limited in luminescent layer, to greatly improve device light emitting efficiency.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention should all
For equivalent substitute mode, it is included within the scope of the present invention.
Claims (10)
1. dialkyl group replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that have following chemical structural formula:
In formula, X is Br or I atom;R is the straight chain or branched alkyl of carbon atom number 1-30.
2. the preparation method that dialkyl group described in claim 1 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that including walking as follows
It is rapid:
(1) under chloroform environment, with bromine by dibenzo [b, d] thiophene bromination at 2- bromine dibenzo [b, d] thiophene;
(2) 2- bromine dibenzo [b, d] thiophene is dissolved in THF, at -70~-80 DEG C, butyl lithium is added dropwise, reaction 2~3 is small
When;Then it maintains the temperature under the conditions of -70~-80 DEG C, 2- isopropoxy -4,4,5,5- tetramethyls -1,3,2- dioxa is added
Then borine is warmed to room temperature reaction 18~24 hours after the reaction was continued 1~2 hour;2- (dibenzo [b, d] thiophene -2- is made
Base) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate;
(3) in toluene solvant, with 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- dioxa boron
Alkane and the bromo- 2- naphthoate of methyl 1- are reaction raw materials, under alkaline environment, using four (triphenylphosphines) conjunction palladium as catalyst,
By Suzuki coupling reaction 12~18 hours at 120~150 DEG C, methyl 1- (dibenzo [b, d] thiophene -2- base) -2- is made
Naphthoate;
(4) methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate is dissolved in THF, methyl-magnesium-bromide is added dropwise,
100~120 DEG C back flow reaction 12~18 hours, be made 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol;
(5) 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol is dissolved in methylene chloride, concentration, which is added dropwise, is
46.5%~48% Eorontrifluoride etherate solution carries out ring closure reaction 1~2 hour at 0~5 DEG C, and 14,14- dioxane is made
Base -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene;
It (6) is oxidant with hydrogen peroxide in acetic acid solvent, by 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes
[1,2-d] thiophene is oxidized to monomer 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy;
(7) 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy is used into bromo in sulfuric acid
Succimide bromination obtains the dialkyl group and replaces naphtho- sulphur dibenzofuran monomer.
3. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step
(1) in, the brominated temperature is no more than 5 DEG C, and the brominated time is 12~18 hours.
4. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step
(2) in, the molar ratio of 2- bromine dibenzo [b, the d] thiophene and butyl lithium is 1:1.5~1:2;The 2- bromine dibenzo [b, d]
The mass ratio of thiophene and 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxaborinate is 1:0.9~1:1.5.
5. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step
(3) in, the 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- dioxaborinate and methyl 1- are bromo-
The molar ratio of 2- naphthoate is 1:1.2~1:1.5;In step (4), the methyl 1- (dibenzo [b, d] thiophene -2- base) -
The molar ratio of 2- naphthoate and methyl-magnesium-bromide is 1:3~1:5.
6. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step
(5) in, the material of 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane -2- base) isopropanol and Eorontrifluoride etherate solution
Liquor ratio is 4:1~4.5:1g/mL.
7. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step
(6) in, the oxidation reaction is reacted 2~5 hours at 100~120 DEG C.
8. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step
(7) in, 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1, the 2-d] thiophene 9,9- dioxy and bromo succinyl
The molar ratio of imines is 1:2~1:2.5;The bromination reaction is reacted 18~24 hours at 0~5 DEG C.
9. replacing the polymer of the structural unit of naphtho- sulphur dibenzofuran monomer containing dialkyl group described in claim 1, which is characterized in that
With following chemical structural formula:
In formula: R is the straight chain or branched alkyl of carbon atom number 1-30, and x, y are molar fraction, 0 < x≤1, x+y=1, polymerization
Spend n=1~300;
Wherein, Ar one of has the following structure:
In formula, R1For the straight chain or branched alkyl of carbon atom number 1-30.
10. polymer as claimed in claim 9 is preparing electroluminescent device, organic photovoltaic cell and organic field effect tube
In application.
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CN107254033A (en) * | 2017-05-18 | 2017-10-17 | 华南理工大学 | Blue light conjugated polymer based on naphtho- 2,7 S, S dioxydibenze bithiophene unit and preparation method and application |
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CN107298757A (en) * | 2017-05-22 | 2017-10-27 | 华南理工大学 | The blue light conjugated polymer of one kind based on naphtho- 8 S, S dioxydibenze bithiophene unit and preparation method and application |
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CN112661743B (en) * | 2020-12-03 | 2023-02-14 | 华南理工大学 | Naphthothiodibenzofuran-based green light micromolecule and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN102850528A (en) * | 2012-05-29 | 2013-01-02 | 华南理工大学 | Luminescent polymer containing S,S-dioxo-dibenzothiophene unit, and application thereof |
CN105924629A (en) * | 2016-06-27 | 2016-09-07 | 华南理工大学 | Conjugated polymer based on naphthoindenofluorene unit as well as preparation method and application thereof |
-
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CN102850528A (en) * | 2012-05-29 | 2013-01-02 | 华南理工大学 | Luminescent polymer containing S,S-dioxo-dibenzothiophene unit, and application thereof |
CN105924629A (en) * | 2016-06-27 | 2016-09-07 | 华南理工大学 | Conjugated polymer based on naphthoindenofluorene unit as well as preparation method and application thereof |
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