CN106366067A - Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer - Google Patents
Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer Download PDFInfo
- Publication number
- CN106366067A CN106366067A CN201610805398.5A CN201610805398A CN106366067A CN 106366067 A CN106366067 A CN 106366067A CN 201610805398 A CN201610805398 A CN 201610805398A CN 106366067 A CN106366067 A CN 106366067A
- Authority
- CN
- China
- Prior art keywords
- oligomer
- dioxydibenze
- unit
- blue
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical group C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 title abstract 6
- 238000000034 method Methods 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000000746 purification Methods 0.000 claims description 23
- 239000003208 petroleum Substances 0.000 claims description 20
- 238000004440 column chromatography Methods 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 229910000085 borane Inorganic materials 0.000 claims description 15
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 15
- 150000002220 fluorenes Chemical group 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000010129 solution processing Methods 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract 2
- 230000003595 spectral effect Effects 0.000 abstract 2
- 238000004458 analytical method Methods 0.000 description 31
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 0 COS1(c(cc(c(*)c2)N)c2-c2c1cc(*)c(*)c2)=O Chemical compound COS1(c(cc(c(*)c2)N)c2-c2c1cc(*)c(*)c2)=O 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 12
- 241000790917 Dioxys <bee> Species 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000001228 spectrum 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-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
- WNEXSUAHKVAPFK-UHFFFAOYSA-N 2,8-dibromodibenzothiophene Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3SC2=C1 WNEXSUAHKVAPFK-UHFFFAOYSA-N 0.000 description 2
- JJUVUIXATPWFND-UHFFFAOYSA-N 3,7-dioctyldibenzothiophene Chemical class C(CCCCCCC)C=1C=CC2=C(SC3=C2C=CC(=C3)CCCCCCCC)C=1 JJUVUIXATPWFND-UHFFFAOYSA-N 0.000 description 2
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical compound [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002027 dichloromethane extract Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- JESBGFNZNSEZMR-UHFFFAOYSA-N 1-bromodibenzothiophene Chemical class S1C2=CC=CC=C2C2=C1C=CC=C2Br JESBGFNZNSEZMR-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- WFUBUHFODBEPNY-UHFFFAOYSA-N 2,8-dioctyldibenzothiophene Chemical class C1=C(CCCCCCCC)C=C2C3=CC(CCCCCCCC)=CC=C3SC2=C1 WFUBUHFODBEPNY-UHFFFAOYSA-N 0.000 description 1
- ITVGRPGDCPNGHZ-UHFFFAOYSA-N 2-bromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 ITVGRPGDCPNGHZ-UHFFFAOYSA-N 0.000 description 1
- NURXGIBWRJKTJO-UHFFFAOYSA-N 2-iodo-9,9-dioctylfluorene Chemical compound C1=C(I)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 NURXGIBWRJKTJO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GQSPCFBGAATOOG-QCDXTXTGSA-N BC(C)(CC(C1C=C2)C=C2Br)/C1=C\CC Chemical compound BC(C)(CC(C1C=C2)C=C2Br)/C1=C\CC GQSPCFBGAATOOG-QCDXTXTGSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- MOCBPXIWBNJCEN-UHFFFAOYSA-N IC1=CC=CC=2C3=CC=CC=C3C(C12)(CCCCCCCC)CCCCCCCC Chemical compound IC1=CC=CC=2C3=CC=CC=C3C(C12)(CCCCCCCC)CCCCCCCC MOCBPXIWBNJCEN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- -1 sucking filtration Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D333/76—Dibenzothiophenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a blue oligomer based on a dibenzothiophene-S,S-dioxide unit and a preparation method and application of the blue oligomer. The blue oligomer is mainly characterized by comprising a fluorene structure unit and the dibenzothiophene-S,S-dioxide structure unit. The preparation method mainly comprises the step of preparation of the blue oligomer based on the dibenzothiophene-S,S-dioxide unit. Due to the fact that the electroluminescence efficiency and the spectral stability are improved by introducing the dibenzothiophene-S,S-dioxide structure unit into the oligomer, the novel oligomer blue-light emitting material is obtained. According to the obtained blue oligomer based on the dibenzothiophene-S,S-dioxide unit, an electroluminescence device prepared through film formation of a solution processing method is high in efficiency, good in spectral stability and suitable for being adopted as a light-emitting layer of a light-emitting diode and a flat-panel displayer.
Description
Technical field
The invention belongs to Organic Light Emitting Diode blue light material technical field, specially it is based on s, s- dioxydibenze bithiophene
Blue oligomer of unit and preparation method and application.
Background technology
Organic Light Emitting Diode (oled) is subject to industrial circle due to it in the potential application of large-area flat-plate display field
Extensive concern with academia.HONGGUANG, green glow and blue light material are to realize three primary colours material necessary to full-color display.In the past
20 years in although electroluminescent organic material achieves considerable progress, but only green light material is in brightness, efficiency and longevity
The requirement of commercialization is reached on life, HONGGUANG and blue light material still are apparent not enough for the requirement of commercialization.This requires that we continue
Go to explore new blue light frequency-doubling, so that its property indices reaches real requirement.
Preparing oled using small molecule emitter material needs using vacuum evaporation production technology so that the product of oled device
Hold at high price, greatly limit the oled competitiveness of product in market.Solution processing be can achieve using polymer luminescent material
Method prepares oled device, significantly reduces the cost of oled product, but due to polymer purification and batches of materials repeatability
The problem of aspect is so that polymer oled device performance is significantly lower than small molecule oled device.Exploitation has small molecule and polymerization concurrently
The oligomer of thing material advantages is expected to, while ensureing device efficiency, reduce element manufacturing cost, thus increasing oled product
The market competitiveness.
S, s- dioxydibenze bithiophene is a short of electricity subelement having many advantages, such as, strong electron-withdrawing group group-so2- determines
Determine its high electron affinity, higher electron mobility, non-oxidizability.By s, s- dioxydibenze bithiophene unit introduces little
In molecule and polymer architecture, show superior electroluminescent properties, its luminescent device is in electric current density and heat treatment temperature
Show superior spectrum stability in the range of degree, cause people and more and more pay close attention to.Exploitation is based on s, s- dioxy two
The oligomer of benzothiophene unit be expected to improve molecular weight, increase its in organic solvent deliquescent simultaneously, realize molten
The high efficiency blue device of liquid processing.
Content of the invention
Present invention aims to the deficiencies in the prior art, one kind is provided to be based on s, s- dioxydibenze bithiophene unit
Blue oligomer.
The present invention also aims to being based on s, the system of the blue oligomer of s- dioxydibenze bithiophene unit described in providing
Preparation Method.
The present invention also aims to provide described be based on s, the answering of the blue oligomer of s- dioxydibenze bithiophene unit
With.Described blueness oligomer efficiency high, spectrum stability is good, is suitable as the luminescent layer of light emitting diode, flat faced display.
The concrete technical scheme of the present invention is as follows.
It is a kind of that based on s, the blue oligomer of s- dioxydibenze bithiophene unit, this oligomer contains fluorene structural units, s,
S- dioxydibenze bithiophene construction unit, described oligomer has a following chemical structural formula 1 or 2:
In formula, r1And r2For the alkyl for 1-20 for the carbon number or h atom；
A is main body construction unit, has one of following chemical structural formula:
In formula, r3For the straight or branched alkyl for 4-20 for the carbon number.
One kind is based on s, the preparation method of the blue oligomer of s- dioxydibenze bithiophene unit, comprises the steps:
By the miscellaneous borine of alkyl fluorenyl epoxy containing a unit and s, s- dioxydibenze thiophthene derivative is dissolved in toluene solvant
In, it is subsequently adding k2co3, tetrabutyl phosphonium bromide aqueous ammonium, add catalyst, reacting by heating under argon protection；After reaction terminates
It is down to room temperature, reactant liquor is extracted, purification, obtain described being based on s, the blue oligomerisation of s- dioxydibenze bithiophene unit
Thing.
Further, described s, s- dioxydibenze thiophthene derivative has a following structural formula:
In formula, r1And r2For the alkyl for 1-20 for the carbon number or h atom.
Further, the described miscellaneous borine of alkyl fluorenyl epoxy containing a unit and s, s- dioxydibenze thiophthene derivative
Mol ratio is 2:1～3:1mol/mol.
Further, described k2co3With s, the mol ratio of s- dioxydibenze thiophthene derivative is 6.5:1～7.5:1mol/
mol.
Further, the concentration of described tetrabutyl phosphonium bromide aqueous ammonium is 20wt%～30wt%, tetrabutyl ammonium bromide water
The addition of solution is 1:3.5～1:14 with the volume ratio of toluene addition.
Further, described catalyst is pd (pph3)4, catalyst pd (pph3)4With s, s- dioxydibenze bithiophene derive
The mol ratio of thing is 0.02:1～0.03:1mol/mol.
Further, the temperature of described reacting by heating is 110～120 DEG C, and the time of reacting by heating is 16～24h.
Further, described extraction is adopted and is extracted with ethyl acetate.
Further, described purification petroleum ether: dichloromethane=5:1～10:1 (v:v) is eluant column chromatography
Methods For Purification.
Described based on s, the blue oligomer of s- dioxydibenze bithiophene unit can be applicable to light emitting diode, flat board shows
Show device.
Described based on s, the blue oligomer of s- dioxydibenze bithiophene unit is applied to light emitting diode, flat pannel display
During device, luminescent layer as light emitting diode, flat faced display, passes through spin coating, inkjet printing or printing process with organic solution
Film forming, its thickness is 50-100 nanometer.
Compared with prior art, the invention has the advantages that and beneficial effect:
(1) of the present invention based on s, the oligomer structure of s- dioxydibenze bithiophene unit is novel；
(2) of the present invention based on s, the oligomer of s- dioxydibenze bithiophene unit can be dissolved in common organic
Solvent, and have fabulous solubility property；
(3) of the present invention based on s, the blue oligomer efficiency high of s- dioxydibenze bithiophene unit, spectrum-stable
Property preferably, extremely pay attention to as light LED material, be particularly well suited as light emitting diode, flat faced display luminous
Layer, is the blue emitting material that a few is hopeful practical application.
Brief description
Fig. 1 is the oligomer 37c8sof4's that embodiment 19 is obtained1H nmr collection of illustrative plates；
Fig. 2 is absorption under filminess for the prepared oligomer 37c8sof4 of embodiment 19 and photoluminescence spectra figure；
Fig. 3 is the thermogravimetric curve of the oligomer 28c8sof4 that embodiment 20 is obtained；
Fig. 4 is the electrochemical profiles of the oligomer 28c8sof4 that embodiment 20 is obtained；
Fig. 5 is electroluminescent light spectrogram under different electric current densities for the prepared oligomer 37sof6 of embodiment 24；
Fig. 6 is photoluminescence spectra figure under filminess for the prepared oligomer 28sof6 of embodiment 25；
Fig. 7 is the thermogravimetric curve of the oligomer 37so36f4 that embodiment 26 is obtained；
Fig. 8 is the electrochemical profiles of the oligomer 28sosf6 that embodiment 27 is obtained.
Specific embodiment
Following examples are only used for the present invention is expanded on further, and do not limit the present invention.
Embodiment 1
The preparation of 2,7- dibromo fluorenes
In the there-necked flask of 1000ml, add fluorenes (60g, 301mmol), iron powder (0.84g, 15mmol) and chloroform
(400ml), ice bath, to 5 DEG C, under the conditions of lucifuge, the mixed liquor of bromine (35ml, 753mmol) and 115ml chloroform is slowly added dropwise
Enter in reaction solution, drip, in room temperature strong stirring (mixing speed is 800rpm) reaction 12 hours.Add toward in reaction bulb
Bisulfite saturated aqueous solution of sodium 200ml is quenched reaction.Reaction mixture is carried out sucking filtration, filtering residue priority saturation bisulfite
Sodium water solution, water and washing with alcohol three times, after filter residue and drying, use chcl3Carry out recrystallization and carry out purification process, obtain white crystalline substance
Body 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.Elementary analysiss 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 of 2,7- bis-
Under argon protection, in 500ml there-necked flask, add 2,7- dibromo fluorenes (32.4g, 100mmol) and dimethyl sub-
Sulfone (250ml), in strong stirring (mixing speed is 800rpm), adds tetrabutyl ammonium bromide (1.61g, 5mmol), Ran Houhuan
Slow Deca sodium hydroxide (40g, 1mol) 50wt% aqueous solution, adds, and reacts 2 hours, property injection 1- bromooctane again
(57.9g,0.3mol).After continuing reaction 10 hours, stopped reaction, reactant liquor is poured into water, adds aqueous hydrochloric acid solution to carry out
Neutralization, with dichloromethane extraction, is washed 7 times with saturated common salt, is dried, after being spin-dried for solvent, with column chromatography method, crude product is entered
Row purification, product petroleum ether purifies as eluant, obtains white solid 43.8g, yield about 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.Elementary analysiss result:
c29h40br2, theoretical value: c, 63.51%；H, 7.31%.Actual measured value: c, 63.53%；H, 7.42%.
Embodiment 3
The preparation of double (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- the base) -9,9- dioctyl fluorene of 2,7-
Under argon protection, in the long there-necked flask of 500ml, add bromo- 9, the 9- dioctyl fluorene (21.9g, 40mmol) of 2,7- bis-
With anhydrous tetrahydro furan 250ml, with liquid nitrogen, reactant liquor is cooled to -78 DEG C, is slowly added dropwise the hexane solution into n-BuLi
(48ml, 2.5m, 120mmol), after stirring 2 hours at keeping -78 DEG C, disposable injection 2- isopropyl -4,4,5,5- tetramethyls -
1,3,2- dioxaborinate (26g, 140mmol), allows it to be naturally warmed to room temperature, and continues reaction 20h.Aqueous ammonium chloride solution is added to quench
Go out reaction, rotary evaporation falls most of solvent, and reactant mixture is poured into water, and with dichloromethane extraction, wash 5 times, separate
Organic faciess, are dried, and filter after being spin-dried for solvent, with column chromatography method (eluant: petroleum ether), crude product are purified, after purification
Obtain white solid 19.8g, yield about 77%.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.Elementary analysiss result: c41h64o4b2, theoretical value: c,
76.73%；H, 10.05%.Actual measured value: c, 76.43%；H, 9.91%.
Embodiment 4
The preparation of 2- bromine fluorenes
In 250ml there-necked flask, add fluorenes (16.6g, 0.1mol), iron powder (88mg, 1.57mmol), chloroform
100ml.Ice-water bath is cooled to 5 DEG C, is slowly added dropwise bromine (17.6g, 0.1mol)/chloroform mixed solution 35ml.During Deca
In reaction bulb, temperature is less than 5 DEG C.After completion of dropping, allow temperature automatically to rise, then react 6 hours at ambient temperature, add
The aqueous solution of sodium bisulfite of saturation is washed till orange red decoloration.Isolate lower floor's white solid, sucking filtration, filtrate and organic be harmonious
And, wash 2 times, remove the iron powder being layered out and residue, the anhydrous mgso of organic layer4It is dried, then filter, chloroform is tied again
Crystalline substance, obtains white solid 19.3g, yield 84%.1h nmr(300mhz,cdcl3) (ppm): 7.90 (d, 1h), 7.79 (d, 1h),
7.72 (s, 1h), 7.55 (d, 2h), 7.38 (s, 1h), 7.28 (s, 1h), 4.10 (d, 2h).13C nmr (75mhz, cdcl3)
(ppm):145.3,143.1,141.0,140.0,133.5,130.6,129.6,128.1,126.7,125.0,122.5,
119.8,35.8.Elementary analysiss result: c13h9Br, theoretical value: c, 63.70%；H, 3.70%.Actual measured value: c,
63.58%；H, 3.55%.
Embodiment 5
The preparation of the bromo- 9,9- dioctyl fluorene of 2- bis-
The preparation of 2-4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- base -9,9- dioctyl fluorene
In there-necked flask add 2- bromine fluorenes (7.4g, 0.03mol), benzyltriethylammoinium chloride (0.07g, 0.3mmol), two
Methyl sulfoxide 90ml and 45ml sodium hydrate aqueous solution (mass percent is 50%).Under room temperature, stirring forms suspension.Deca
1- bromine normal hexane (12.5g, 65mmol), after continuing stirring 3 hours, is extracted with ether.Wash second with saturated sodium-chloride water solution
Ether phase, anhydrous magnesium sulfate is dried.Boil off solvent, product petroleum ether makees the purification of eluant column chromatography, obtains white solid, yield
89%.1h nmr(300mhz,cdcl3) (ppm): 7.90 (d, 1h), 7.79 (s, 1h), 7.72 (s, 1h), 7.55 (d, 2h),
7.38 (s, 1h), 7.28 (s, 1h), 1.84 (d, 4h), 1.30 (d, 4h), 1.26-1.01 (m, 20h), 0.80 (t, 6h).13c
Nmr (75mhz, cdcl3)(ppm):150.0,147.8,141.0,140.0,133.5,130.6,129.6,126.7,122.5,
123.2,121.6,52.2,43.9,31.9,30.2,29.6,29.3,24.4,22.7,14.1.Elementary analysiss result:
c29h41Br, theoretical value: c, 74.18%；H, 8.80%.Actual measured value: c, 74.02%；H, 8.65%.
Embodiment 6
4,4,5,5- tetramethyl -2- (9,9,9 ', 9 '-four octyl group -9h-9 ' h- [2,2 '-connect fluorenes] -7- base) -1,3,2- bis-
The preparation of oxa- borine
Under an argon atmosphere, bromo- for 2- 9,9- dioctyl fluorene (14.1g, 0.03mol) is dissolved in the thf that 180ml refines
In, gradually Deca 1.6mol l at -78 DEG C-1N-BuLi 25ml, keep -78 DEG C of low temperature under the conditions of, react 2 hours, so
Add 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxaborinate 25ml afterwards, at -78 DEG C, continue reaction 1 hour,
It is slowly increased to room temperature reaction 24 hours.Reactant mixture is poured into water, is extracted with ethyl acetate, organic layer is complete with saline solution
After washing, plus anhydrous magnesium sulfate is dried.After solution concentrates, obtain thick pale yellow shape crude product, purify (eluting with silica gel column chromatography
Agent selects petrol ether/ethyl acetate=20/1, v/v), product is placed freezing in refrigerator for a long time and is obtained white solid, yield
70%.1h nmr(300mhz,cdcl3) (ppm): 7.90 (d, 2h), 7.33 (d, 2h), 7.16 (d, 2h), 7.06 (s, 1h),
1.83 (m, 4h), 1.29 (d, 4h), 1.26 (m, 20h), 1.20 (m, 12h), 0.88 (t, 6h).13C nmr (75mhz, cdcl3)
(ppm):147.8,141.0,133.1,130.9,129.6,128.4,126.7,123.2,121.6,88.1,43.9,31.9,
29.6,29.3,24.7,24.4,22.7,14.1.Elementary analysiss result: c35h53bo2, theoretical value: c, 81.37%；h,
10.34%.Actual measured value: c, 81.25%；H, 10.20%.
Embodiment 7
4,4,5,5- tetramethyl -2- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [2,2 '-connect fluorenyl] -7- base) -1,3,2-
The preparation of the miscellaneous borine of epoxy
Double (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- the base) -9,9- dioctyl fluorene of 2,7- (1.39g,
2.17mmol) it is dissolved in 45ml toluene solvant with the bromo- 9,9- dioctyl fluorene (1.02g, 2.17mmol) of 2,7- bis-, be subsequently adding
k2co3(1.50g, 10.86mmol), tetrabutyl ammonium bromide (35mg, 108.58umol) and 5ml water, add catalyst pd
(pph3)4(50.19mg, 43.43umol), after being then heated to 110 DEG C of reaction 16h under argon protection, is down to room temperature, reaction
Liquid is extracted with ethyl acetate, with petroleum ether: dichloromethane=1:1 is the Methods For Purification of eluant column chromatography, yield 80%.1h
nmr(300mhz,cdcl3) (ppm): 8.09 (d, 2h), 7.90 (d, 2h), 7.89 (s, 1h), 7.78 (d, 2h), 7.67 (s,
1h),7.55(s,1h),7.38(d,1h),7.33(d,1h),7.28(s,1h),7.16(d,1h),1.83(m,8h),1.29
(dd,8h),1.26(m,40h),1.20(m,12h),0.88(t,12h).13C nmr (75mhz, cdcl3)(ppm):148.3,
147.8,141.2,141.0,139.9,134.8,133.1,130.9,130.5,129.6,128.9,128.4,126.7,
124.7,123.2,121.6,88.1,53.6,43.9,31.9,30.2,29.6,29.3,24.7,22.7,14.1.Elementary analysiss
Result: c64h93bo2, theoretical value: c, 84.92%；H, 10.36%.Actual measured value: c, 84.78%；H, 10.19%.
Embodiment 8
The preparation of 2,8- dibromo dibenzothiophen
Dibenzothiophen (5.0g, 0.027mol) is dissolved in 30ml chloroform the there-necked flask of 150ml.At 0 DEG C
Deca bromine (3.1ml, 0.061mol), room temperature reaction 16h under nitrogen atmosphere, then wash by filtration of crude product and with methanol,
Obtain white powder material, yield 85%.1h nmr(300mhz,cdcl3)(ppm):7.92(d,2h),7.86(d,2h),
7.45(d,2h).13C nmr (75mhz, cdcl3) (ppm): 135.1,132.6,129.2,127.1,125.0,118.9.Element
Analysis result: c12h6br2S, theoretical value: c, 42.14%；H, 1.77%.Actual measured value: c, 41.02%；H, 1.63%.
Embodiment 9
The preparation of the bromo- s of 2,8- bis-, s- dioxydibenze bithiophene
2,8- dibromo dibenzothiophen (9.2g, 0.03mol) is dissolved in 450ml petroleum ether the there-necked flask of 500ml, in room
Lower point of temperature adds formic acid and hydrogen peroxide (concentration is 30%) each 40ml for 4 times.After reacting 2 hours at 40 DEG C, it is heated to 70 DEG C instead
Answer 20h.The white powder obtaining is cooled, filter, be washed to neutrality, is dried, uses chlorobenzene recrystallization, obtain needle-like solid, produces
Rate 90%.1h nmr(300mhz,cdcl3)(ppm):7.86(d,2h),7.84(d,2h),7.62(d,2h).13c nmr
(75mhz, cdcl3)(ppm):136.6,134.5,132.9,131.5,131.0,127.2.Elementary analysiss result:
c12h6br2o2S, theoretical value: c, 38.53%；H, 1.62%.Actual measured value: c, 38.39%；H, 1.47%.
Embodiment 10
The preparation of s, s- dioxydibenze bithiophene
In the three neck round bottom flask of 500ml, add dibenzothiophen (18.4g, 100mmol), acetic acid (200ml) and hydrogen peroxide
(50ml), it is heated to reflux lower reaction 24h, reaction terminates rear question response temperature and drops to room temperature, and reactant liquor separates out a large amount of crystal, takes out
Filter, uses acetic acid and washing with alcohol filtering residue 3 times successively.Dry, obtain colourless acicular crystal product, yield 80%.1h nmr
(300mhz,cdcl3) δ (ppm): 7.52-7.56 (m, 2h), 7.63-7.67 (m, 2h), 7.80-7.85 (m, 4h).13c nmr
(75mhz,cdcl3) δ (ppm): 121.58,122.16,130.17,131.60,133.87,137.73.Elementary analysiss result
(c12h8so2), theoretical value: c, 66.64%；H, 3.72%；S, 14.82%；O, 14.81%.Actual measured value: c, 66.81%；
H, 3.53%；S, 14.74%；O 14.77%.
Embodiment 11
The preparation of the bromo- s of 3,7- bis-, s- dioxydibenze bithiophene
In the single-necked flask of 500ml, addition s, s- dioxydibenze bithiophene (10.8g, 50mmol), sulphuric acid (200ml),
It is slowly added to n- bromo-succinimide (nbs) (21.41g, 120mmol) under stirring.Reaction 12 hours, reactant is poured into ice
In water, a large amount of solids are had to separate out, sucking filtration, filtering residue uses each washing of sodium bicarbonate aqueous solution, water and ethanol 3 times successively, is dried, filtering residue
Carry out recrystallization with chlorobenzene, obtain colourless acicular crystal 9.4g, yield: 50%.1h nmr(300mhz,cdcl3) δ (ppm): 8.26
(d, 2h), 7.83 (d, 2h), 7.62 (d, 2h).13c nmr(300mhz,cdcl3) δ (ppm): 139.8,137.1,131.1,
131.0,129.7,123.0.Elementary analysiss result (c12h6br2o2S), theoretical value: c, 38.53%；H, 1.62%.Practical measurement
Value: c, 38.42%；H, 1.48%.
Embodiment 12
The preparation of the bromo- dibenzothiophenes of 2,8- bis-
Dibenzothiophen (5.0g, 0.027mol) is dissolved in 30ml chloroform the there-necked flask of 150ml.At 0 DEG C
Deca bromine (15ml, 0.061mol), room temperature reaction 16h under nitrogen atmosphere, then washs by filtration of crude product and with methanol, obtains
To white powder material, yield: 80%.1h nmr(300mhz,cdcl3)δ(ppm):7.58(m,2h),7.71(m,2h),
8.24(m,2h).Elementary analysiss result: c12h6br2S, theoretical value: c, 42.14%；H, 1.77%.Actual measured value: c,
41.01%；H, 1.62%.
Embodiment 13
The preparation of 2,8- dioctyls-dibenzothiophenes
By bromo- for 2,8- bis- dibenzothiophenes (6.48g, 20mmol) and 1g ni (dppp) cl2It is dissolved in the anhydrous tetrahydrochysene of 200ml
Furan, lucifuge, 10 DEG C of Deca c well prepared in advance8h17The diethyl ether solution (45mmol) of mgbr.After being added dropwise to complete, remove ice bath,
Room temperature reaction 2h, with the nh of saturation4Cl removes unnecessary grignard reagent, and dichloromethane extracts, and magnesium sulfate is dried.With petroleum ether it is
Eluant carries out column chromatography, obtains colourless liquid, yield: 85%.1h nmr(300mhz,cdcl3)δ(ppm):8.04(d,2h),
7.81(d,2h),7.33(dd,2h),2.85(t,4h),1.80(m,4h),1.53-1.38(br,20h),0.99(t,6h).Unit
Plain analysis result: c28h40S, value of calculation: c, 82.29%, h, 9.87%, s, 7.85%；Test value: c, 82.34%, h,
9.95%, s, 7.71%.
Embodiment 14
2,8- dioctyl-s, the preparation of s- dioxo-dibenzothiophene
2,8- dioctyl-dibenzothiophenes (4.08g, 10mmol) are dissolved in 30ml acetic acid, add 10ml h2o2,100
DEG C reaction 2h.Solvent, recrystallizing methanol are evaporated off, obtain white solid, yield: 90%.1h nmr(300mhz,cdcl3)δ(ppm):
7.71(d,2h),7.59(s,2h),7.32(dd,2h),2.73(t,4h),1.68(m,4h),1.35-1.29(br,20h),
0.90(t,6h).Elementary analysiss result: c28h40o2S, value of calculation: c, 76.36%, h, 9.09%, o, 7.27%, s, 7.27%；
Test value: c, 75.97%, h, 9.35%, o, 7.38%, s, 7.30%.
Embodiment 15
The bromo- 2,8- dioctyl-s of 3,7- bis-, the preparation of s- dioxydibenze bithiophene
By 2,8- dioctyl-s, s- dioxo-dibenzothiophene (2.2g, 5mmol) is dissolved in 100ml sulphuric acid, lucifuge, adds
Nbs, reacts 24h under room temperature.After reaction terminates, it is added slowly in frozen water, filter, and with washing with alcohol 3 times.With oil
Ether/dichloromethane=1:1 carries out column chromatography for eluant, obtains white solid, yield: 40%.1h nmr(300mhz,cdcl3)
δ(ppm):7.93(s,2h),7.59(s,2h),2.84(t,4h),1.67(m,4h),1.35-1.28(br,20h),0.91(t,
6h).Elementary analysiss result: c28h38o2sbr2, value of calculation: c, 56.19%, h, 6.35%, o, 5.35%, s, 5.36%；Test
Value: c, 56.21%, h, 6.42%, o, 5.43%, s, 5.32%.
Embodiment 16
The preparation of 3,7- dioctyl-dibenzothiophenes
By bromo- for 3,7- bis- dibenzothiophenes (6.48g, 20mmol) and 1g ni (dppp) cl2It is dissolved in the anhydrous tetrahydrochysene of 200ml
Furan, lucifuge, 10 DEG C of Deca c well prepared in advance8h17The diethyl ether solution (45mmol) of mgbr.After being added dropwise to complete, remove ice bath,
Room temperature reaction 2h, with the nh of saturation4Cl removes unnecessary grignard reagent, and dichloromethane extracts, and magnesium sulfate is dried.With petroleum ether it is
Eluant carries out column chromatography, obtains colourless liquid, yield: 82%.1h nmr(300mhz,cdcl3)δ(ppm):8.05(s,2h),
7.78(s,2h),7.32(s,2h),2.64(d,4h),1.61(m,4h),1.26(br,20h),0.91(t,6h).Elementary analysiss
Result: c28h40S, value of calculation: c, 82.29%, h, 9.87%；Test value: c, 82.11%, h, 9.70%.
Embodiment 17
3,7- dioctyl-s, the preparation of s- dioxo-dibenzothiophene
3,7- dioctyl-dibenzothiophenes (4.08g, 10mmol) are dissolved in 30ml acetic acid, add 10ml h2o2,100
DEG C reaction 2h.Solvent, recrystallizing methanol are evaporated off, obtain white solid, yield: 85%.1h nmr(300mhz,cdcl3)δ(ppm):
7.94(s,2h),7.89(s,2h),7.32(s,2h),2.64(d,4h),1.61(m,4h),1.26(br,20h),0.91(t,
6h).Elementary analysiss result: c28h40o2S, value of calculation: c, 76.31%, h, 9.15%；Test value: c, 76.16%, h, 9.01%.
Embodiment 18
The bromo- 3,7- dioctyl-s of 2,8- bis-, the preparation of s- dioxydibenze bithiophene
By 3,7- dioctyl-s, s- dioxo-dibenzothiophene (2.2g, 5mmol) is dissolved in 30ml chloroform.0
Deca bromine (3ml, 12mmol) at DEG C, room temperature reaction 16h under nitrogen atmosphere, then wash by filtration of crude product and with methanol,
After drying, column chromatography is carried out for eluant with petroleum ether/dichloromethane=1:1, obtains white solid, yield: 78%.1h nmr
(300mhz,cdcl3)δ(ppm):7.78(s,2h),7.62(s,2h),2.63(d,4h),1.59(m,4h),1.26(br,
20h),0.89(t,6h).Elementary analysiss result: c28h38br2o2S, value of calculation: c, 56.19%, h, 6.40%；Test value: c,
56.01%, h, 6.23%.
Embodiment 19
3,7- bis- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [2,2 '-company fluorenyl] -7- base) 2,8- dioctyl-dibenzo
The preparation of [b, d] thiophene 5,5- dioxy (37c8sof4)
4,4,5,5- tetramethyl -2- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [2,2 '-connect fluorenyl] -7- base) -1,3,2-
The miscellaneous borine of epoxy (3.93g, 4.34mmol) and the bromo- 2,8- dioctyl-s of 3,7- bis-, s- dioxydibenze bithiophene (1.30g,
2.17mmol) it is dissolved in 80ml toluene solvant, be subsequently adding k2co3(1.95g, 14.1mmol), 20wt% tetrabutyl ammonium bromide
Aqueous solution 6ml, adds catalyst pd (pph3)4(50.19mg, 43.4umol), is then heated to 110 DEG C instead under argon protection
After answering 16h, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=5:1 (v/v) is eluant post layer
The Methods For Purification of analysis, yield 75%.1h nmr(300mhz,cdcl3)(ppm):8.18(d,2h),7.93(d,2h),7.82(d,
2h),7.73(m,6h),7.38(d,2h),7.36(m,13h),7.30(d,6h),2.13-1.99(m,21h),1.21-1.09
(m,112h),0.83(m,28h),0.72(t,20h).Elementary analysiss result: c144h200o2S, theoretical value: c, 86.69%；h,
10.10%.Actual measured value: c, 86.03%；H, 9.68%.Lower Fig. 1 gives oligomer 37c8sof4's1H nmr collection of illustrative plates,
Can determine from figure synthesis final material be desired 37c8sof4.It is thin in solid that Fig. 2 gives oligomer 37c8sof4
Ultraviolet-visible absorption spectroscopy under membrane stage and photoluminescence spectra.As can be seen from Figure 2, the maximum absorption band of oligomer 37c8sof4
At 214nm and 383nm, luminescence generated by light maximum emission peak is located at 468nm.
Embodiment 20
2,8- bis- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [2,2 '-connect fluorenyl] -7- base) 3,7- dioctyl-dibenzo
The preparation of [b, d] thiophene 5,5- dioxy (28c8sof4)
4,4,5,5- tetramethyl -2- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [2,2 '-connect fluorenyl] -7- base) -1,3,2-
The miscellaneous borine of epoxy (5.89g, 6.51mmol) and the bromo- 3,7- dioctyl-s of 2,8- bis-, s- titanium dioxide dibenzothiophen (1.30g,
2.17mmol) it is dissolved in 30ml toluene solvant, be subsequently adding k2co3(2.25g, 16.28mmol), 30wt% tetrabutyl phosphonium bromide
Aqueous ammonium 8ml, adds catalyst pd (pph3)4(75.22mg, 65.1umol), is then heated to 120 DEG C under argon protection
After reaction 24h, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=10:1 (v/v) is eluant
The Methods For Purification of column chromatography, yield 72%.1h nmr(300mhz,cdcl3)(ppm):8.14(d,2h),8.11(d,2h),8.09
(dd,6h),7.89(m,8h),7.78(dd,6h),7.55(s,2h),7.38(d,2h),7.28(d,2h),7.25(s,2h),
1.83(dd,20h),1.29(t,40h),1.26(m,80h),0.88(t,30h).Elementary analysiss result: c144h200o2S, theoretical
Value: c, 86.69%；H, 10.10%.Actual measured value: c, 86.17%；H, 9.91%.Lower Fig. 3 gives oligomer
The thermogravimetric curve figure of 28c8sof4, as can be known from Figure, the heat decomposition temperature of oligomer 28c8sof4, at 405 DEG C, illustrates that this is neat
Polymers has the high heat stability of comparison.Lower Fig. 4 gives the electro-chemical test curve of oligomer 28c8sof4, can from this curve
Know, the oxidizing potential of oligomer 28c8sof4 is located at 1.45v.
Embodiment 21
The preparation of the bromo- 7- of 2- iodo- 9,9- dioctyl fluorene
In there-necked flask, add 2- bromo- 9,9- dioctyl fluorene (2.83g, 6.02mmol), i2(1g, 3.2mmol), h5io6
(0.2g, 0.88mmol), in 150ml 80wt% acetum, after stirring half an hour, under nitrogen protection, is to slowly warm up to 80
DEG C reaction 4 hours.It is subsequently cooled to room temperature, after revolving removes all solvents, can get brown solid crude product.Crude product is molten
Solution, in toluene, uses 5wt%nahso3Aqueous solution washes 3 times.After concentrated solvent, do the purification of eluant column chromatography method with toluene,
Then use re crystallization from toluene, can get pure product.Yield 65%.1h nmr(300mhz,cdcl3)(ppm):7.93(d,1h),
7.79(s,1h),7.76(d,1h),7.72(s,1h),7.67(d,1h),7.55(d,1h),1.83(d,4h),1.29(d,4h),
1.26(m,20h),0.88(t,6h).13c nmr(300mhz,cdcl3)(ppm):150.0,149.4,140.0,139.9,
139.6,135.6,133.5,130.6,130.0,129.6,122.5,93.7,51.3,43.9,31.9,30.2,29.6,29.3,
24.4,22.7,14.1.Elementary analysiss result: c29h40Bri, theoretical value: c, 58.50%；H, 6.77%.Actual measured value: c,
58.38%；H, 6.61%.
Embodiment 22
Bromo- 9,9,9 ', 9 '-four octyl group -9h of 7-, the preparation of 9 ' h-2,2 '-company's fluorenes
2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- base) -9,9- dioctyl fluorene (1.12g, 2.17mmol)
The iodo- 9,9- dioctyl fluorene (1.29g, 2.17mmol) of 7- bromo- with 2- is dissolved in 40ml toluene solvant, is subsequently adding k2co3
(1.50g, 10.86mmol), tetrabutyl ammonium bromide (35mg, 108.58umol) and 5ml water, add catalyst pd (pph3)4
(50.19mg, 43.43umol), after being then heated to 110 DEG C of reaction 16h under argon protection, is down to room temperature, reactant liquor second
Acetoacetic ester extracts, the Methods For Purification being eluant column chromatography with petroleum ether, yield 74%.1h nmr(300mhz,cdcl3)
(ppm):8.09(d,2h),7.90(s,1h),7.88(d,2h),7.79(s,1h),7.77(s,2h),7.72(s,1h),7.55
(d,2h),7.38(s,1h),7.28(s,1h),1.83(m,8h),1.29(m,8h),1.26(m,40h),0.88(t,12h).13c
Nmr (75mhz, cdcl3)(ppm):150.0,148.3,147.8,141.1,139.9,133.5,130.5,129.6,128.9,
126.7,124.7,123.2,122.5,121.6,43.9,31.9,30.2,29.6,29.3,24.4,22.7,14.1.Element divides
Analysis result: c58h81Br, theoretical value: c, 81.18%；H, 9.51%.Actual measured value: c, 80.02%；H, 9.34%.
Embodiment 23
2- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h, 9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three fluorenyls] -7- base) -4,4,5,
The preparation of the miscellaneous borine of 5- tetramethyl -1,3,2- epoxy
Double (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- the base) -9,9- dioctyl fluorene of 2,7- (1.39g,
2.17mmol) it is dissolved in 50ml first with bromo- 9,9,9 ', 9 " of 7--four octyl group -9h, 9 ' h-2,2 '-company's fluorenes (1.86g, 2.17mmol)
In benzene solvent, it is subsequently adding k2co3(1.50g, 10.86mmol), tetrabutyl ammonium bromide (35mg, 108.58umol) and 5ml water,
Add catalyst pd (pph3)4(50.19mg, 43.43umol), after being then heated to 110 DEG C of reaction 16h under argon protection, fall
To room temperature, reactant liquor is extracted with ethyl acetate, the Methods For Purification being eluant column chromatography with petroleum ether, yield 67%.1h nmr
(300mhz,cdcl3)(ppm):8.09(dd,4h),7.90(d,2h),7.88(t,3h),7.78(dd,4h),7.67(s,1h),
7.55(s,1h),7.38(s,1h),7.33(s,1h),7.28(s,1h),7.16(s,1h),1.83(m,12h),1.29(m,
12h),1.26(60h),1.20(t,12h),0.88(m,18h).Elementary analysiss result: c93h133bo2, theoretical value: c,
86.33%；H, 10.36%.
Actual measured value: c, 86.21%；H, 10.26%.
Embodiment 24
3,7- bis- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h-9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three fluorenyls] -7- base) two
The preparation of benzo [b, d] thiophene 5,5- dioxy (37sof6)
2- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h, 9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three fluorenyls] -7- base) -4,4,5,
The miscellaneous borine of 5- tetramethyl -1,3,2- epoxy (7.01g, 5.43mmol) and the bromo- s of 3,7- bis-, s- dioxydibenze bithiophene (0.81g,
2.17mmol) it is dissolved in 80ml toluene solvant, be subsequently adding k2co3(2.10g, 15.2mmol), 25wt% tetrabutyl ammonium bromide
Aqueous solution 7ml, adds catalyst pd (pph3)4(62.69mg, 54.25umol), is then heated to 115 DEG C instead under argon protection
After answering 20h, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=8:1 (v:v) is eluant post layer
The Methods For Purification of analysis, yield 60%.1h nmr(300mhz,cdcl3)(ppm):8.43(d,2h),8.13(d,2h),8.09(m,
10h),7.92(s,2h),7.89(m,10h),7.78(m,10h),7.55(d,2h),7.38(s,2h),7.28(s,2h),7.25
(s,2h),1.83(m,24h),1.29(m,24h),1.26(m,120h),0.88(t,36h).Elementary analysiss result:
c186h248o2S, theoretical value: c, 87.68%；H, 9.81%.Actual measured value: c, 87.49%；H, 9.70%.Lower Fig. 5 gives
Oligomer 37sof6 is in 12macm-2～400ma cm-2Electroluminescent light spectrogram in current density range, knowable to this figure, with
Being gradually increased of electric current density, el spectrum is not changed in, illustrate that its spectrum stability is fabulous.
Embodiment 25
2,8- bis- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h-9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three fluorenyls] -7- base) two
The preparation of benzo [b, d] thiophene 5,5- dioxy (28sof6)
2- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h, 9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three fluorenyls] -7- base) -4,4,5,
The miscellaneous borine of 5- tetramethyl -1,3,2- epoxy (5.63g, 4.34mmol) and the bromo- s of 2,8- bis-, s- dioxydibenze bithiophene (0.81g,
2.17mmol) it is dissolved in 80ml toluene solvant, be subsequently adding k2co3(1.95g, 14.1mmol), 20wt% tetrabutyl ammonium bromide
Aqueous solution 6ml water, adds catalyst pd (pph3)4(50.19mg, 43.4umol), is then heated to 110 DEG C under argon protection
After reaction 16h, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=5:1 (v:v) is eluant post
The Methods For Purification of chromatography, yield 60%.1h nmr(300mhz,cdcl3)(ppm):8.37(d,2h),8.10(d,2h),8.03
(m,10h),7.90(s,2h),7.85(m,10h),7.78(m,10h),7.55(d,2h),7.38(s,2h),7.28(s,2h),
7.25(s,2h),1.83(m,24h),1.29(m,24h),1.26(m,120h),0.88(t,36h).Elementary analysiss result:
c186h248o2S, theoretical value: c, 87.68%；H, 9.81%.Actual measured value: c, 87.49%；H, 9.70%.Lower Fig. 6 gives
Photoluminescence spectra figure under filminess for the oligomer 28sof6.Knowable to this figure, maximum emission peak position setting in 437nm,
Vibration peak is located at 465nm.
Embodiment 26
3,7- bis- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [3,3 '-company fluorenyl] -6- base) dibenzo [b, d] thiophene 5,5-
The preparation of dioxy (37so36f4)
4,4,5,5- tetramethyl -2- (9,9,9 ', 9 '-four octyl group -9h, 9 ' h- [3,3 '-connect fluorenyl] -6- base) -1,3,2-
The miscellaneous borine of epoxy (4.92g, 5.43mmol) and the bromo- s of 3,7- bis-, s- dioxydibenze bithiophene (0.81g, 2.17mmol) is dissolved in
In 80ml toluene solvant, it is subsequently adding k2co3(2.25g, 16.28mmol), 30wt% tetrabutyl phosphonium bromide aqueous ammonium 8ml, add
Catalyst pd (pph3)4(75.22mg, 65.1umol), after being then heated to 120 DEG C of reaction 24h under argon protection, is down to room
Temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=10:1 (v/v) is the Methods For Purification of eluant column chromatography,
Yield 79%.1h nmr(300mhz,cdcl3)(ppm):8.24(d,2h),7.97(d,2h),7.83(d,2h),7.75(m,
6h),7.39(d,2h),7.34(m,13h),7.28(d,6h),2.10-1.88(m,17h),1.20-1.05(m,88h),0.80
(m,28h),0.71(t,14h).Elementary analysiss result: c128h168o2S, theoretical value: c, 86.82%；H, 9.56%.Practical measurement
Value: c, 84.74%；H, 9.41%.Lower Fig. 7 gives the thermogravimetric curve of oligomer 37so36f4, as seen from the figure, this oligomer
Heat decomposition temperature be 380 DEG C, illustrate that this oligomer has good heat stability.
Embodiment 27
2,8- bis- (2,7,2 ', 7 ', 2 ", 7 "-dioctyl -9,9,9 ', 9 ', 9 " and, 9 "-spiral shell two fluorenes -9h-9 ' h, 9 " h- [2,
2 ': 7 ', 2 "-three fluorenyls] -7- base) dibenzo [b, d] thiophene 5,5- dioxy (28sosf6) preparation
2- (2 ', 2 " ', 2 " " ', 7 ', 7 " ', 7 " " '-six octyl group -2,2 ": 7 ", 2 " "-three (9,9 '-spiral shell two [fluorenes] -7-
Base)) -- the miscellaneous borine of 4,4,5,5- tetramethyl -1,3,2- epoxy (11.36g, 6.51mmol) and the bromo- s of 2,8- bis-, s- dioxydibenze
Bithiophene (0.81g, 2.17mmol) is dissolved in 80ml toluene solvant, is subsequently adding k2co3(2.10g,15.2mmol),
25wt% tetrabutyl phosphonium bromide aqueous ammonium 7ml, adds catalyst pd (pph3)4(62.69mg, 54.25umol), then in argon
After being heated to 110 DEG C of reaction 16h under protection, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=
8:1 (v:v) is the Methods For Purification of eluant column chromatography, yield 60%.1h nmr(300mhz,cdcl3)(ppm):7.89(td,
20h),8.08(t,8h),7.86(d,4h),7.84(d,4h),7.78(d,4h),7.73(d,4h),7.62(d,2h),7.50
(s,4h),7.42(td,8h),7.37(d,4h),7.33(d,4h),7.28(d,2h),7.25(td,8h),7.20(d,4h),
2.64(m,24h),1.61(s,24h),1.29(m,144h),0.88(m,36h).Elementary analysiss result: c258h284o2S, theoretical
Value: c, 89.84%；H, 8.30%.Actual measured value: c, 88.26%；H, 8.12%.Lower Fig. 8 gives oligomer 28sosf6
Electro-chemical test curve, would know that from this curve, the oxidizing potential of oligomer 28sosf6 is located at 1.41v.
Embodiment 28
3- (12- methyl -6,6,6 ', 6 ', 12,12 ', 12 '-eight octyl group -6,6 ', 12,12 '-tetrahydrochysene-[2,2 '-connect indole
[1,2-b] fluorenes] -8- base) -7- (12 '-methyl -6,6-6 ', 6 ', 12,12 '-eight octyl groups -6,6 ', 12,12 '-tetrahydrochysene-[2,2 ' -
Even indole [1,2-b] fluorenes] -8- base) dibenzo [b, d] thiophene 5,5- dioxy (37soif4) preparation
4,4,5,5- tetramethyl -2- (6,6,6 ', 6 ', 12,12,12 ', 12 '-eight octyl groups -6,6 ', 12,12 '-tetrahydrochysene-[2,
2 '-two indole [1,2-b] fluorenes] -8- base) -1, the miscellaneous borine of 3,2- epoxies (6.64g, 4.34mmol) and the bromo- s of 3,7- bis-, s- dioxy
Dibenzothiophenes (0.81g, 2.17mmol) are dissolved in 80ml toluene solvant, are subsequently adding k2co3(2.07g,15mmol),
25wt% tetrabutyl phosphonium bromide aqueous ammonium 8ml, adds catalyst pd (pph3)4(50.19mg, 43.4umol), then protects in argon
After being heated to 110 DEG C of reaction 16h under shield, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=8:1
(v:v) for the Methods For Purification of eluant column chromatography, yield 50%.1h nmr(300mhz,cdcl3)(ppm):8.29(d,2h),
8.26(dd,4h),8.07(d,4h),7.98(dd,4h),7.90(d,8h),7.87(d,4h),7.83(d,2h),7.64(d,
4h),7.60(d,2h),7.47(d,4h),7.33(d,2h),1.83(m,32h),1.29(m,192h),0.88(t,48h).Unit
Plain analysis result: c220h312o2S, theoretical value: c, 87.47%；H, 10.41%.Actual measured value: c, 86.89%；h,
10.25%.
Embodiment 29
3,7- bis- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h-9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three silicon fluorene bases] -7- base)
The preparation of dibenzo [b, d] thiophene 5,5- dioxy (37sosif6)
2- (9,9,9 ', 9 ', 9 ", 9 "-six octyl group -9h, 9 ' h, 9 " h- [2,2 ': 7 ', 2 "-three silicon fluorene bases] -7- base) -4,4,
The miscellaneous borine of 5,5- tetramethyl -1,3,2- epoxy (5.82g, 4.34mmol) and the bromo- s of 3,7- bis-, s- dioxydibenze bithiophene
(0.81g, 2.17mmol) is dissolved in 80ml toluene solvant, is subsequently adding k2co3(2.07g, 15mmol), the 20wt% tetrabutyl
Bromination aqueous ammonium 8ml, adds catalyst pd (pph3)4(50.19mg, 43.4umol), is then heated under argon protection
After 115 DEG C of reaction 18h, it is down to room temperature, reactant liquor is extracted with ethyl acetate, with petroleum ether: dichloromethane=7:1 (v:v) is to wash
The Methods For Purification of de- agent column chromatography, yield 60%.1h nmr(300mhz,cdcl3)(ppm):8.43(d,2h),8.13(d,2h),
8.09(m,10h),7.92(s,2h),7.89(m,10h),7.78(m,10h),7.55(d,2h),7.38(s,2h),7.28(s,
2h),7.25(s,2h),1.83(m,24h),1.29(m,24h),1.26(m,120h),0.88(t,36h).Elementary analysiss result:
c180h248o2Ssi, theoretical value: c, 81.75%；H, 9.45%.Actual measured value: c, 81.59%；H, 9.31%.
Embodiment 30
The preparation of the electroluminescent device based on oligomer 37c8sof4
On tin indium oxide (ito) glass of well in advance, its square resistance is 20 ω/, first uses acetone, washing successively
Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes.On ito, spin coating is mixed polystyrolsulfon acid
Polyethoxy thiophene (pedot:pss) film, thickness is 150nm.It is dried 8 hours at 80 DEG C in vacuum drying oven of pedot:pss film.
Subsequently the xylene solution (1wt%) of oligomer 37c8sof4 is spin-coated on the surface of pedot:pss film, thickness is 80nm；?
A thin layer csf (1.5nm) and the metal al layer of 120nm thickness are deposited with successively afterwards on luminescent layer.
Based on single layer device structure: ito/pedot:pss/emitter/csf/al, the max-flow of oligomer 37c8sof4
Obvious results rate is 1.5cd/a, and maximum external quantum efficiency is 1.8%, and chromaticity coordinates is (0.16,0.17), due to single layer device structure, empty
The potential barrier of the electron injection in cave is higher, and the transmission of hole and electronics is uneven, so performance is relatively low, needs to device
It is further optimized.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplifying all should
For equivalent substitute mode, it is included within protection scope of the present invention.
Claims (10)
1. a kind of be based on s, the blue oligomer of s- dioxydibenze bithiophene unit it is characterised in that this oligomer contain fluorene structured
Unit, s, s- dioxydibenze bithiophene construction unit, described oligomer has a following chemical structural formula 1 or 2:
In formula, r1And r2For the alkyl for 1-20 for the carbon number or h atom；
A is main body construction unit, has one of following chemical structural formula:
In formula, r3For the straight chain for 4-20 for the carbon number or branched alkyl.
2. the one kind described in claim 1 be based on s, the preparation method of the blue oligomer of s- dioxydibenze bithiophene unit, its
It is characterised by comprising the steps:
By the alkyl fluorenes ring oxa- borine containing a unit and s, s- dioxydibenze thiophthene derivative is dissolved in toluene solvant, so
Add k afterwards2co3, tetrabutyl phosphonium bromide aqueous ammonium, add catalyst, reacting by heating under argon protection；Reaction is down to after terminating
Room temperature, extracts to reactant liquor, purification, obtains described being based on s, the blue oligomer of s- dioxydibenze bithiophene unit.
3. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
It is characterised in that described s, s- dioxydibenze thiophthene derivative has a following structural formula to method:
In formula, r1And r2For the alkyl for 1-20 for the carbon number or h atom.
4. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
Method is it is characterised in that the described alkyl fluorenes ring oxa- borine containing a unit and s, the mol ratio of s- dioxydibenze thiophthene derivative
For 2:1～3:1mol/mol.
5. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
Method is it is characterised in that described k2co3With s, the mol ratio of s- dioxydibenze thiophthene derivative is 6.5:1～7.5:1mol/
mol.
6. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
Method it is characterised in that described tetrabutyl phosphonium bromide aqueous ammonium concentration be 20wt%～30wt%, tetrabutyl phosphonium bromide aqueous ammonium
The volume ratio of addition and toluene addition be 1:3.5～1:14.
7. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
Method is it is characterised in that described catalyst is pd (pph3)4, catalyst pd (pph3)4With s, s- dioxydibenze thiophthene derivative
Mol ratio be 0.02:1～0.03:1mol/mol.
8. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
It is characterised in that the temperature of described reacting by heating is 110～120 DEG C, the time of reacting by heating is 16～24h to method.
9. one kind according to claim 2 is based on s, the preparation side of the blue oligomer of s- dioxydibenze bithiophene unit
Method is it is characterised in that described extraction is adopted and is extracted with ethyl acetate；Described purification is to use petroleum ether: dichloromethane=5:1～10:1
(v:v) for the Methods For Purification of eluant column chromatography.
10. the one kind described in claim 1 is based on s, the blue oligomer of s- dioxydibenze bithiophene unit light emitting diode,
Application in flat faced display it is characterised in that described based on s, the blue oligomer of s- dioxydibenze bithiophene unit is used as
Light emitting diode, the luminescent layer of flat faced display, pass through spin coating, inkjet printing or printing process film forming, thickness with organic solution
For 50-100 nanometer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610805398.5A CN106366067A (en) | 2016-09-06 | 2016-09-06 | Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610805398.5A CN106366067A (en) | 2016-09-06 | 2016-09-06 | Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106366067A true CN106366067A (en) | 2017-02-01 |
Family
ID=57900099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610805398.5A Pending CN106366067A (en) | 2016-09-06 | 2016-09-06 | Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366067A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200831A (en) * | 2017-02-24 | 2017-09-26 | 华南理工大学 | A kind of polyfluorene class conjugated polymer for containing aromatic group based on side chain and preparation method and application |
| CN107602529A (en) * | 2017-08-30 | 2018-01-19 | 华南理工大学 | It is a kind of to contain S, the compound of S dioxydibenze bithiophene units and preparation method and application with strong two-photon effect |
| CN109705087A (en) * | 2017-10-25 | 2019-05-03 | 华南协同创新研究院 | Cyclic oligomers of the derivative containing dibenzothiophene unit and the preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712674A (en) * | 2009-11-13 | 2010-05-26 | 华南理工大学 | Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof |
| CN102417587A (en) * | 2011-11-04 | 2012-04-18 | 华南理工大学 | Electro-phosphorescence polymer containing (alkyl-substituted-)S,S- dioxo-dibenzothiophene unit and application thereof |
| CN105001233A (en) * | 2015-04-23 | 2015-10-28 | 华南理工大学 | Bis S,S-dioxo-dibenzothiophene five-membered ring monomer, preparation method thereof and polymer |
-
2016
- 2016-09-06 CN CN201610805398.5A patent/CN106366067A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712674A (en) * | 2009-11-13 | 2010-05-26 | 华南理工大学 | Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof |
| CN102417587A (en) * | 2011-11-04 | 2012-04-18 | 华南理工大学 | Electro-phosphorescence polymer containing (alkyl-substituted-)S,S- dioxo-dibenzothiophene unit and application thereof |
| CN105001233A (en) * | 2015-04-23 | 2015-10-28 | 华南理工大学 | Bis S,S-dioxo-dibenzothiophene five-membered ring monomer, preparation method thereof and polymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200831A (en) * | 2017-02-24 | 2017-09-26 | 华南理工大学 | A kind of polyfluorene class conjugated polymer for containing aromatic group based on side chain and preparation method and application |
| CN107602529A (en) * | 2017-08-30 | 2018-01-19 | 华南理工大学 | It is a kind of to contain S, the compound of S dioxydibenze bithiophene units and preparation method and application with strong two-photon effect |
| CN109705087A (en) * | 2017-10-25 | 2019-05-03 | 华南协同创新研究院 | Cyclic oligomers of the derivative containing dibenzothiophene unit and the preparation method and application thereof |
| CN109705087B (en) * | 2017-10-25 | 2020-06-05 | 华南协同创新研究院 | Annular oligomer containing dibenzothiophene unit derivative and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243329B (en) | One kind being based on S, and S- dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and the preparation method and application thereof to receptor type | |
| CN103833507B (en) | A series of electroluminescent organic materials and preparation method and application | |
| CN106117524B (en) | A kind of thermal activation delayed fluorescence conjugated polymer luminescent material of side chain group containing sulfuryl and the preparation method and application thereof | |
| CN103194215B (en) | Preparation method of aggregation-induced emission molecule | |
| CN106588869B (en) | 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 | |
| CN107011269A (en) | Bipolarity small molecule emitter material using spiro fluorene unit as core of environmentally friendly solvent processing and preparation method and application can be used | |
| CN103709380B (en) | Three fluorenamine polymer luminescent material and preparation method and application | |
| CN109400590A (en) | Thermal activation delayed fluorescent material and application thereof in organic light-emitting diode | |
| CN105503846B (en) | One kind being based on the bipolarity small molecule emitter material and the preparation method and application thereof of 4- (9H- carbazole -9- base) aniline | |
| CN106366067A (en) | Blue oligomer based on dibenzothiophene-S,S-dioxide unit and preparation method and application of blue oligomer | |
| CN106905513A (en) | Based on two heteroaromatics and 3,7 S, the conjugated polymer of S dioxydibenze bithiophene units and preparation method and application | |
| CN107286175A (en) | A kind of star bipolarity small molecule emitter material using triaryl amine group as core and preparation method and application | |
| CN106866940A (en) | A kind of conjugated polymer for being based on 3,7 naphtho- sulphur dibenzofuran units and preparation method and application | |
| CN106946878A (en) | Bipolarity luminescent material using alkyl phenanthroline unit as core of environmentally friendly solvent processing and preparation method and application can be used | |
| CN102807554B (en) | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof | |
| CN106866938A (en) | A kind of conjugated polymer based on naphthalene two and indenes fluorenes unit and preparation method and application | |
| CN106190107A (en) | Luminescent material and preparation method thereof and the Organic Light Emitting Diode using this luminescent material | |
| CN103554444B (en) | A kind of white light polymer materials and preparation method thereof and application | |
| CN102807556B (en) | Organic semiconductor material containing naphthalene, anthracene, dibenzothiophene sulfone units and preparation method and application thereof | |
| CN107353891A (en) | It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application | |
| CN108948015A (en) | A kind of pyrene derivatives and its organic electroluminescence device | |
| CN107954921A (en) | A kind of electroluminescent material blocked with 9- phenyl fluorenes and preparation method and application | |
| CN106883386A (en) | A kind of conjugated polymer based on heteroaromatic and indenes fluorenes unit and preparation method and application | |
| CN106699746A (en) | Bipolar small molecular light-emitting material based on naphthothiodibenzofuran unit as well as preparation method and application of bipolar small molecular light-emitting material | |
| CN111647141A (en) | Organic electroluminescent material based on thienopyrrole and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170201 |