CN106854252A - The design synthesis of one class new bipolar polymer host material and its performance study - Google Patents
The design synthesis of one class new bipolar polymer host material and its performance study Download PDFInfo
- Publication number
- CN106854252A CN106854252A CN201710012237.5A CN201710012237A CN106854252A CN 106854252 A CN106854252 A CN 106854252A CN 201710012237 A CN201710012237 A CN 201710012237A CN 106854252 A CN106854252 A CN 106854252A
- Authority
- CN
- China
- Prior art keywords
- carbazole
- monomers
- nitrogen
- reaction
- dried
- 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
- 239000000463 material Substances 0.000 title claims abstract description 76
- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 238000013461 design Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title abstract description 24
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 19
- 239000012043 crude product Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- VCDOOGZTWDOHEB-UHFFFAOYSA-N 1-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Br)=CC=C2 VCDOOGZTWDOHEB-UHFFFAOYSA-N 0.000 claims description 6
- 238000003811 acetone extraction Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 4
- FUMINOMBBQKZOH-UHFFFAOYSA-N 1-(2-chloroethyl)-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCCl FUMINOMBBQKZOH-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- NDQKGYXNMLOECO-UHFFFAOYSA-N acetic acid;potassium Chemical compound [K].CC(O)=O NDQKGYXNMLOECO-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000012467 final product Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- DBWGAXVWWNKFNI-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 DBWGAXVWWNKFNI-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenylpropanol Natural products OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- OZVRXSGTNWILMN-UHFFFAOYSA-N Ic1ccccc1-c(cccc1)c1I Chemical compound Ic1ccccc1-c(cccc1)c1I OZVRXSGTNWILMN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-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
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/12—N-Vinylcarbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
Abstract
The invention belongs to organic optoelectronic material technical field, and in particular to a class is based on design synthesis and its performance study of the new bipolar polymer host material of carbazole.The material is, using PVK as molecular skeleton, the mobility of hole and electronics to be balanced by introducing electron withdraw group, and using the material in organic light emitting diode device field, obtains efficient device performance.
Description
Technical field
The invention belongs to organic photoelectrical material technical field.A specifically related to class new bipolar polymer host material
Design synthesis and its performance study, can be applied to organic light emission using such material as material of main part and the doping of object phosphor material
The organic electronic such as diode field.
Background technology
Organic electro phosphorescent device (PHOLEDs) exists due to introducing heavy metal complex illuminator between heavy metal
Spin-spin interaction interaction, singlet and triplet excitons can be simultaneously captured, nearly 100% can be obtained in theory
Internal quantum efficiency, have potential application value on extensive device and flexible device.Heavy metal in PHOLEDs is matched somebody with somebody
Compound phosphor material separately as luminescent layer, but generally can not be entrained in suitable material of main part, forms Subjective and Objective
Luminescence system, to weaken the excessive quenching effect for causing of metal complex concentration and triplet state-triplet state (T1-T1) bury in oblivion effect,
So as to improve the efficiency of device.Therefore the material of main part of design synthesized high-performance is also particularly important for PHOLEDs.Small point
Using complicated evaporation coating technique in preparation process, cumbersome preparation process and the cost of costliness are greatly limited sub- PHOLEDs
The further development and commercialization of product；And electrostrictive polymer phosphorescent device (PPLEDs) then uses simple in preparation process
The methods such as the solution processing method of low cost, such as spin coating and inkjet printing, are conducive to the manufacture that large area flexible shows.Therefore,
Develop the polymer host material of function admirable for PPLEDs, be the crucial problem of a comparing.
PVK (PVK) as a quasi-representative, better performances non-co- yoke type polymer, due to containing higher
ETThe cavity transmission ability become reconciled, is applied in PPLEDs by wide coverage as material of main part.According to So etc., it is based on
The energy efficiency and luminous efficiency of the double-layer blue light PhPLEDs of PVK and FIrpic can reach 14lm/W and 22cd/A.But
The electronic transmission performance and thermal stability of PVK are not highly desirable, and high-performance, longevity are being prepared as polymer host material
There is certain limitation on the PPLEDs of life；And the report of the polymer host material of related non-conjugated class formation is still little.
The stronger functional group of electron-withdrawing power is introduced into PVK, the transmittability for obtaining electronics and hole is piled up compared with the bipolarity of balance
Polymer host material, can obtain more preferable progress in blue phosphorescent PPLEDs directions.Still be necessary to enter in this field
The more thoroughgoing and painstaking research work of row.In view of this, we intend by the method for functionalization, by some have special steric hindrance,
The electrophilic functional group of electronic structure is incorporated into model accumulation polymer, design synthesis a series of new bipolarity heap accumulation
Compound material of main part.Primary study difference electron withdraw group piles up the E of polymer to modelT, thermodynamic stability, electric charge transmission
The regulation and control of performance, photophysical property and electrochemical properties.Inquire into bipolarity and pile up the molecular structure of polymer, photoelectric property, thin
Relation between film pattern and device performance.On this basis, a series of high performance polymer material of main parts are filtered out, is hair
Exhibition blueness PPLEDs provides the support of principle and material.On the basis of optimization of material, with reference to device optimization process, device is studied
In basic physical mechanism, the inherent operation principle of device is disclosed, so as to instruct the design of new device with application.Please join in detail
Document (1) Shiyang Shao, Junqiao Ding, Tengling Ye, Zhiyuan Xie, Lixiang Wang are read,
Xiabin Jing, and Fosong Wang Adv.Mater.2011,23,3570-3574. documents (2) Ho-Hsiu Chou,
Chien-Hong Cheng Adv.Mater.2010,22,2468-2471. documents (3) Mounggon Kim, Jun Yeob Lee
Adv.Funct.Mater.2014,24,4164-4169.
The content of the invention
It is an object of the invention to pass through to be introduced toward on the carbazole avtive spot of the PVK (PVK) of non-co- yoke type
The electrophilic functional group of different structure builds new bipolar polymer host material, using the material in organic light emission
The application in diode component field obtains efficient device performance.
New bipolar polymer host material in the present invention, its design feature is mainly the polyethylene toward non-co- yoke type
The electrophilic functional group of different structure is introduced on the carbazole avtive spot of base carbazole (PVK).Its structural features are as follows：
Wherein：R is electron withdraw group, and the connection site of R is its of 1,2,3 and No. 4 positions of carbazole unit in compound I and II
One of；X, y and n are Any Digit in 1~1000.
R is specially the one kind in having structure：
The preparation method of heretofore described new bipolar polymer host material, the VCz replaced by R
Monomer carries out radically homo or copolyreaction is prepared, specific as follows：
Wherein, x, y and n are Any Digit in 1~1000.
Raolical polymerizable is under the conditions of 85 DEG C of temperature, with azodiisobutyronitrile AIBN as catalyst, to R substitutions
Vinylcabazole monomers carry out polymerisation.The reaction bulb used in experiment need to soak and clean in potassium bichromate washing lotion, connect
The salt deposit that inwall is removed with the water vapour of saturation, is finally toasted in flame and is protected cooling with nitrogen, reach removing absorption
The purpose of the oxygen in bottle wall.Under nitrogen protection, prepare R substitution vinylcabazole monomers or configuration VCz and
The mixture concentration of the vinylcabazole monomers of R substitutions is 0.1~1.0mol/L, and AIBN concentration is 1.0~10.0 × 10-3mol/
The toluene or tetrahydrofuran solution of L, drum nitrogen are stirred evenly.Above-mentioned configuration solution is separately added into reaction bulb, liquid nitrogen cooling takes out true
Sky, thawed inflated with nitrogen again, and then envelope bottle is inserted in 85 DEG C of oil bath pans of constant temperature, and reaction 72h is quenched reaction after terminating using methyl alcohol, so
Methyl alcohol sedimentation afterwards obtains polymer crude product, and crude product acetone extraction obtains polymeric material.
The preparation method of heretofore described class new polymers bipolar host material, it is characterised in that the R takes
The vinylcabazole monomers in generation are that the carbazole monomers replaced by R are prepared respectively through nucleophilic displacement of fluorine and elimination reaction, R substitutions
Carbazole monomers can by bromo carbazole be raw material by two kinds difference routes prepare, it is specific as follows：
Step a by bromo carbazole and R-H, palladium, 1, after 1 '-bis- Diphenyl phosphino ferrocenes (dppf), triethylamine mixing
After adding dmso solution, the back flow reaction 12h under lucifuge and nitrogen guard mode.Reaction is extracted after terminating with dichloromethane
Take out organic phase.Organic phase is dried using anhydrous magnesium sulfate, organic solution is rotated after filtering, obtained using column chromatography for separation method
The carbazole monomers of R substitutions；
Step a ' by raw material bromo carbazole and connection boric acid pinacol ester, palladium, 1, double (diphenylphosphine) ferrocene of 1- and
Potassium acetate is added in dry dimethyl sulfoxide (DMSO), under the protection of nitrogen, 90 DEG C is heated to while stirring, reacts 12h, is stood afterwards
Room temperature is cooled to, is extracted with water and dichloromethane, then dried with anhydrous magnesium sulfate, filtering, and remove organic solvent, obtain whole product
Thing crude product；And post purifying is crossed, obtain the borate of carbazole；
Step b ' by the borate of carbazole and R-X (X is halogen) and tetrakis triphenylphosphine palladium be added to toluene, ethanol and
In the mixed solution of 2M wet chemicals, under the protection of nitrogen, side stirring change is heated to 90 DEG C, reacts 12h, stands afterwards cold
But to room temperature, extracted with water and dichloromethane, then dried with anhydrous magnesium sulfate, filtering, and remove organic solvent, obtain product thick
Product；And post purifying is crossed, obtain the carbazole monomers of R substitutions；
The carbazole monomers that step c replaces above-mentioned R are added to 1,2- with potassium carbonate, potassium hydroxide and TBAB
In dichloroethanes, 5h is reacted under the conditions of 50 DEG C, stand be cooled to room temperature afterwards, extracted with water and dichloromethane, then use anhydrous sulphur
Sour magnesium is dried, filtering, and removes organic solvent, obtains product crude product；And post purifying is crossed, obtain the chloroethyl carbazole list of R substitutions
Body；
The chloroethyl carbazole monomers that step d replaces R obtained above are added to isopropyl with potassium hydroxide, hydroquinones
In the mixed solution of alcohol and toluene, 3h is reacted under the conditions of 85 DEG C, stand be cooled to room temperature afterwards, solvent is spin-dried for, with water and dichloro
Methane is extracted, then is dried with anhydrous magnesium sulfate, filtering, and removes organic solvent, obtains product crude product；And post purifying is crossed, obtain
Final monomer.
The application of heretofore described new bipolar polymer host material, it is characterised in that the material and phosphorescent guest
It is applied in organic electroluminescence device as luminescent layer after luminescent material doping.Structure in organic electro phosphorescent device is：
Transparent anode/hole transmission layer/polymer host material and phosphorescent guest luminescent material/electron transfer layer/metallic cathode, light
Compound of the material of main part of layer as described in right 1, guest materials is metal complex phosphor material.
Beneficial effects of the present invention are：
(1) design, synthesis and its application the invention provides a class new bipolar polymer host material, possess conjunction
Suitable triplet and the charge transport ability of balance, for the preparation of high-efficiency polymer electro phosphorescent device provides condition；
(2) Bipolar Polymer material of main part synthetic method of the present invention is simple, is suitable for extensive use；
(3) Bipolar Polymer material of main part of the present invention, with good thermodynamic stability and film forming；
(4) Bipolar Polymer material of main part of the present invention, can effectively be mixed with phosphorescent guest material material
It is miscellaneous, luminescent device is prepared using solution spin-coating method, be conducive to the manufacture that large area flexible shows.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, with example of the invention
It is used to explain the present invention together, is not construed as limiting the invention.Preferred embodiment is in the accompanying drawings in embodiment.
Ultraviolet-ray visible absorbing and the fluorescent spectroscopic properties contrast of Fig. 1 polymer P VPOK, PVPOK-1 and PVPOK-2 films
Figure；
The antenna effect spectrum comparison diagram of Fig. 2 polymer Ps VPOK, PVPOK-1 and PVPOK-2；
The cyclic voltammetry curve figure of Fig. 3 polymer Ps VK and PVPOK-1, PVPOK-2 and PVPOK；
The TGA curves and DSC curve figure of Fig. 4 polymer Ps VPOK；
Fig. 5 electro phosphorescent device structure charts；
The electroluminescent light spectrogram of Fig. 6 polymer Ps VK and PVPOK-1, PVPOK-2 device；
Fig. 7 polymer Ps VK and PVPOK-1, PVPOK-2 blue phosphorescent device property figure.
Specific embodiment
The present invention is further described below by specific embodiment, but the invention is not limited in these embodiments.
The synthesis of the PVPOK of example 1；
The synthesis of intermediate (2)：By compound 2 (1.83g, 7.4mmol) and diphenyl phosphorus oxygen (1g, 4.5mmol), acetic acid
Palladium (0.056g, 0.25mmol), 1,1 '-bis- Diphenyl phosphino ferrocenes (dppf) (0.25g, 0.45mmol), triethylamine (0.8mL,
After dimethyl sulfoxide (DMSO) (15mL) dissolving is added after 5.9mmol) mixing, the back flow reaction 12h under lucifuge and nitrogen guard mode.Instead
After should terminating organic phase is extracted with dichloromethane.Organic phase is dried using anhydrous magnesium sulfate, organic solution is rotated after filtering,
Product Compound 2 is obtained using column chromatography for separation method.
The synthesis of intermediate (3)：At 50 DEG C, by compound 2 (3.67g, 10mmol), potassium hydroxide (2.25g,
40mol), potassium carbonate (13.82g, 100mmol), TBAB (0.32mg, 1mmol) is dissolved in 1,2- dichloroethanes
3~5h is reacted in (100mL) in single-necked flask.Reaction removes solid in solution after terminating, and is extracted using dichloromethane, anhydrous
Magnesium sulfate dries organic phase, and method acquisition compound 4 is used column chromatography after being spin-dried for organic solvent.
The synthesis of intermediate (4)：Compound 3 (4.3g, 10mmol) and potassium hydroxide (4.5g, 80mmol), hydroquinones
(0.11g, 1mmol), toluene (10mL) and isopropanol (100mL) flow back 3h at 85 DEG C.Reaction is spin-dried for toluene and different after terminating
Propyl alcohol, and extracted with dichloromethane, anhydrous magnesium sulfate is dried, filtering, and compound 4 is obtained using column chromatography for separation method after being spin-dried for.
The synthesis of final product PVPOK：Monomeric compound 4 (0.2g, 0.5mmol) is added to be dissolved in through metal in reaction tube
Sodium is dried and in distilled tetrahydrofuran (1mL), and the vinyl polymerization initiator azo two for adding monomer weight ratio to be 1% is different
Butyronitrile (2.0mg), is stirred at reflux 3 days at 85 DEG C.Reaction is quenched reaction after terminating using methyl alcohol, and then petroleum ether sedimentation is obtained
Polymer crude product, crude product acetone extraction obtains polymeric material PVPOK.
The synthesis of the copolymer p VPOK-1 of example 2 and PVPOK-2；
The synthesis of polymer P VPOK-1 and PVPOK-2：Monomeric compound 5 (0.1g, 0.25mmol/ are added in reaction tube
0.2g, 0.5mmol) and 9- VCzs (0.196g, 1mmol/0.098g, 0.5mmol) with mol ratio be 8: 2 or 5: 5
Ratio mixes, and corresponds to add total monomer weight than the polymerization initiator azodiisobutyronitrile (2.96mg/ for 1% respectively
2.98mg), anhydrous and oxygen-free environment in reaction tube is kept, the tetrahydrofuran (2.5mL/2mL) by water removal deoxygenation treatment is added, is treated
After in the complete solvent of monomer and solution, 60 DEG C of initiated polymerizations under the conditions of lucifuge.After the completion of polymerization triggers, system is placed in 85
Reacted 3 days at DEG C.Reaction is quenched reaction after terminating using methyl alcohol, and then petroleum ether sedimentation obtains polymer crude product, crude product
With acetone extraction, obtain polymeric material and obtain copolymer p VPOK-1 and PVPOK-2.
The synthesis of example 3 PV (2-PO) K；
The synthesis of intermediate (2)：By compound 2 (1.83g, 7.4mmol) and diphenyl phosphorus oxygen (1g, 4.5mmol), acetic acid
Palladium (0.056g, 0.25mmol), 1,1 '-bis- Diphenyl phosphino ferrocenes (dppf) (0.25g, 0.45mmol), triethylamine (0.8mL,
After dimethyl sulfoxide (DMSO) (15mL) dissolving is added after 5.9mmol) mixing, the back flow reaction 12h under lucifuge and nitrogen guard mode.Instead
After should terminating organic phase is extracted with dichloromethane.Organic phase is dried using anhydrous magnesium sulfate, organic solution is rotated after filtering,
Product Compound 2 is obtained using column chromatography for separation method.
The synthesis of intermediate (3)：At 50 DEG C, by compound 2 (3.67g, 10mmol), potassium hydroxide (2.25g,
40mol), potassium carbonate (13.82g, 100mmol), TBAB (0.32mg, 1mmol) is dissolved in 1,2- dichloroethanes
3~5h is reacted in (100mL) in single-necked flask.Reaction removes solid in solution after terminating, and is extracted using dichloromethane, anhydrous
Magnesium sulfate dries organic phase, and method acquisition compound 4 is used column chromatography after being spin-dried for organic solvent.
The synthesis of intermediate (4)：Compound 3 (4.3g, 10mmol) and potassium hydroxide (4.5g, 80mmol), hydroquinones
(0.11g, 1mmol), toluene (10mL) and isopropanol (100mL) flow back 3h at 85 DEG C.Reaction is spin-dried for toluene and different after terminating
Propyl alcohol, and extracted with dichloromethane, anhydrous magnesium sulfate is dried, filtering, and compound 4 is obtained using column chromatography for separation method after being spin-dried for.
The synthesis of final product PV (2-PO) K：In reaction tube add monomeric compound 4 (0.2g, 0.5mmol) be dissolved in through
Metallic sodium is dried and in distilled tetrahydrofuran (1mL), adds the vinyl polymerization initiator azo that monomer weight ratio is 1%
Bis-isobutyronitrile (2.0mg), is stirred at reflux 3 days at 85 DEG C.Reaction is quenched reaction after terminating using methyl alcohol, then petroleum ether sedimentation
Polymer crude product is obtained, crude product acetone extraction obtains polymeric material PV (2-PO) K.
The synthesis of the PVDPTK of embodiment 4；
The synthesis of intermediate (2)：By 3- bromines carbazole (4.92g, 20mmol) and connection boric acid pinacol ester (6.6g,
26mmol), double (diphenylphosphine) ferrocene (0.66g, 1.2mmol) of palladium (0.134g, 0.6mmol), 1,1- and potassium acetate
(5.88g, 60mmol) is added in dry dimethyl sulfoxide (DMSO), under the protection of nitrogen, 90 DEG C, reaction is heated to while stirring
12h, stands be cooled to room temperature afterwards, is extracted with dichloromethane, then is dried with anhydrous magnesium sulfate, and filtering is spin-dried for organic solvent, obtains
Crude product；And post purifying is crossed, obtain intermediate product 5.
The synthesis of intermediate (3)：By intermediate product 3 (0.586g, 2mmol), chloro- 4, the 6- diphenyl -1,3,5-triazines of 2-
(0.536g, 2mmol) and tetrakis triphenylphosphine palladium (0,023g, 0.02mmol) are added to wet chemical (9mL), the first of 2M
(18mL, v/v=2: in mixed solution 1), under the protection of nitrogen, react 12h, reaction knot to benzene/ethanol under the conditions of 110 DEG C
Room temperature is cooled to after beam, is extracted with dichloromethane, then dried with anhydrous magnesium sulfate, filtering is spin-dried for organic solvent, is slightly produced
Thing；And post purifying is crossed, obtain intermediate product 6.
The synthesis of intermediate (4)：At 50 DEG C, by intermediate product 3 (0.398g, 1mmol), potassium hydroxide (0.225g,
4mmol), potassium carbonate (1.382g, 10mmol), TBAB (0.032g, 0.1mmol) is dissolved in 1,2- dichloroethanes
5h is reacted in single-necked flask in (10mL).Reaction removes solid in solution after terminating, dichloromethane extraction, anhydrous magnesium sulfate is done
Dry organic phase, filtering after being spin-dried for organic solvent, uses column chromatography method and obtains intermediate product 7.
The synthesis of intermediate (5)：By intermediate product 4 (4.61g, 10mmol) and potassium hydroxide (4.49g, 80mmol), right
Benzenediol (0.11g, 1mmol), toluene (10mL) and isopropanol (100mL) flow back 3h at 85 DEG C.Reaction is spin-dried for first after terminating
Benzene and isopropanol, and extracted with dichloromethane, anhydrous magnesium sulfate dries organic phase, filters, and after being spin-dried for organic solvent, uses column chromatography
Partition method obtains monomer 8.
The synthesis of final product PVDPTK：Monomeric compound 5 (0.2g, 0.45mmol) is added to be dissolved in through gold in reaction tube
Category sodium is dried and in distilled tetrahydrofuran (1mL), adds the vinyl polymerization initiator azo two that monomer weight ratio is 1%
Isobutyronitrile (2.0mg), is stirred at reflux 3 days at 85 DEG C.Reaction is quenched reaction after terminating using methyl alcohol, and then methyl alcohol sedimentation is obtained
Polymer crude product, crude product acetone extraction obtains polymeric material PVDPTK.
The measure of the polymeric material photophysical property of embodiment 5；
A ultraviolet-visible absorption spectroscopies：The toluene solution of prepared polymer in cuvette, concentration is about 1 × 10-5Mol/L,
Inhaled using Shimadzu (Shimadzu) UV-1750 ultraviolet-visual spectrometers and Hitachi (Hitachi) F-4600 XRFs
Receive spectrum and emission spectrometry.Wherein, the instrument that film preparation is used is the KW- of Chinese Academy of Sciences Microelectronics Institute's research and development
4A type spin coating instrument；
B fluorescence emission spectrums：The fluorescence emission spectrum (solution and film) of all material is tested in Hitachi F-
4600 spectrometers, test sample compound concentration is 1 × 10-5mol L-1Toluene solution, excitation wavelength be ultravioletvisible absorption light
The maximum wavelength of spectrum.Wherein, the instrument that film preparation is used is the KW-4A type spin coatings of Chinese Academy of Sciences Microelectronics Institute's research and development
Instrument；
C antenna effect emission spectrum：Antenna effect emission spectrum is tested in Hitachi F-4600 spectrometers, cold in liquid nitrogen
But under the conditions of, material temperature reaches 77K, and material is configured into 1 × 10-5mol L-1Toluene solution test.
The measure of the polymeric material electrochemical properties of embodiment 6；
The electrochemical properties of polymer host material are determined with electrochemical cyclic voltammetry (CV), and laboratory apparatus is
Occasion China CHI660E electrochemical workstations, the instrument uses three-electrode system, including glass carbon working electrode, Ag/AgCl references
Electrode and platinum filament are to electrode.Polymer electrochemical determines the solvent for using and is generally dry acetonitrile, and electrolyte is hexafluoro phosphorus
TBuA (Bu4NPF6), concentration is 0.1M；Test environment needs nitrogen to protect.The speed of instrument scanning is 0.1V/s, benchmark
Thing is ferrocene (FOC), calculates HOMO the and LUMO energy of the material by measuring the beginning voltage of oxidation and reduction process respectively
Level.
The measure of the polymeric material thermodynamic stability of embodiment 7；
Differential scanning (DSC) is tested：DSC collection of illustrative plates is tested in Shimadzu DSC-60A differential thermals view, in nitrogen protective condition
Under, sample is heated to the state less than decomposition temperature with the speed of 10 DEG C/min first, then, lowers the temperature under the conditions of liquid nitrogen and returns to
Initial temperature, for the second time again with the speed heating scan of 10 DEG C/min.
Thermogravimetric (TGA) is tested：TGA collection of illustrative plates is tested in Shimadzu DTG-60H Instruments, under nitrogen protective condition, is risen
Warm speed is 10 DEG C/min, while the flow velocity of protection air-flow nitrogen is 20cm3/min, material weight changes until reaching perseverance
Weight state.
The preparation of the electroluminescent blue phosphorescent device of the polymeric material of embodiment 8 and sign；
New bipolar electro-phosphorescent main body material of the invention is applied to luminescent layer, in organic electro phosphorescent device
Structure is：Transparent anode/hole transmission layer/subject and object luminescent material/electron transfer layer/negative electrode, luminescent layer is by main body material
Material and dopant material composition, the compound of the material of main part of luminescent layer as described in right 1, guest materials is metal complex phosphorescence
Material.
The blue PhPLEDs device architectures prepared as material of main part are ITO/PEDOT：PSS(40nm)/Host：10-
15wt%FIrpic (100nm)/TPBI (20nm)/LiF (0.8nm)/Al (100nm).Wherein ITO is that square resistance is 10-20
The transparency electrode of Ω；PEDOT：PSS is poly- (3,4- ethylenedioxythiophene)/poly- (p styrene sulfonic acid) as hole transport material
Material, Host：FIrpic is ((4, the 6- difluoros of iridium (III) two of Bipolar Polymer material of main part doping 10-15% in embodiment
Benzene)-pyridine-N, C2′) picolinic acid ester, using solution spin coating technique, film thickness is 100nm；LiF cushions are deposited with again, most
Afterwards, evaporating Al negative electrode.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvement can also be made, these improvement are also considered as protection of the invention
Scope.
Claims (4)
1. a class new bipolar polymer host material, its design feature is mainly the PVK toward non-co- yoke type
(PVK) the electrophilic functional group of different structure is introduced on carbazole avtive spot.Its structural features are as follows：
Wherein：R is electron withdraw group, in compound I and II the connection site of R be 1,2,3 and No. 4 positions of carbazole unit wherein it
One；X, y and n are Any Digit in 1~1000.
R is specially the one kind in having structure：
2. a kind of preparation method of class new bipolar polymer host material as claimed in claim 1, it is characterised in that
By R replace vinylcabazole monomers carry out radically homo or mix with vinylcabazole monomers carry out it is free-radical polymerized
Obtain, it is specific as follows：
Wherein, x, y and n are Any Digit in 1~1000.
Raolical polymerizable is under the conditions of 85 DEG C of temperature, with azodiisobutyronitrile AIBN as catalyst, to the ethene of R substitutions
Base carbazole monomers carry out polymerisation.The reaction bulb used in experiment need to soak and clean in potassium bichromate washing lotion, then use
The water vapour of saturation removes the salt deposit of inwall, is finally toasted in flame and protects cooling with nitrogen, reaches removing absorption in bottle
The purpose of the oxygen on wall.Under nitrogen protection, the vinylcabazole monomers or configuration VCz and R for preparing R substitutions take
The mixture concentration of the vinylcabazole monomers in generation is 0.1~1.0mol/L, and AIBN concentration is 1.0~10.0 × 10-3Mol/L's
Toluene or tetrahydrofuran solution, drum nitrogen are stirred evenly.Above-mentioned configuration solution is separately added into reaction bulb, liquid nitrogen cooling is vacuumized,
Thawed inflated with nitrogen again, and then envelope bottle is inserted in 85 DEG C of oil bath pans of constant temperature, and reaction 72h is quenched reaction after terminating using methyl alcohol, then
Methyl alcohol sedimentation obtains polymer crude product, and crude product acetone extraction obtains polymeric material.
3. the preparation method of a class new polymers bipolar host material according to claim 2, it is characterised in that the R
Substituted vinylcabazole monomers are that the carbazole monomers replaced by R are prepared respectively through nucleophilic displacement of fluorine and elimination reaction, and R takes
The carbazole monomers in generation can be that raw material is prepared by two kinds of different routes by bromo carbazole, specific as follows：
Step a adds bromo carbazole and R-H, palladium, 1 after 1 '-bis- Diphenyl phosphino ferrocenes (dppf), triethylamine mixing
After dmso solution, the back flow reaction 12h under lucifuge and nitrogen guard mode.Reaction is extracted after terminating with dichloromethane
Organic phase.Organic phase is dried using anhydrous magnesium sulfate, organic solution is rotated after filtering, obtaining R using column chromatography for separation method takes
The carbazole monomers in generation；
Step a ' by raw material bromo carbazole and connection boric acid pinacol ester, palladium, 1, double (diphenylphosphine) ferrocene of 1- and acetic acid
Potassium is added in dry dimethyl sulfoxide (DMSO), under the protection of nitrogen, 90 DEG C is heated to while stirring, reacts 12h, and cooling is stood afterwards
To room temperature, extracted with water and dichloromethane, then dried with anhydrous magnesium sulfate, filtering, and remove organic solvent, obtain end-product thick
Product；And post purifying is crossed, obtain the borate of carbazole；
The borate of carbazole and R-X (X is halogen) and tetrakis triphenylphosphine palladium are added to toluene, ethanol and 2M carbon by step b '
In the mixed solution of sour aqueous solutions of potassium, under the protection of nitrogen, side stirring change is heated to 90 DEG C, reacts 12h, stands be cooled to afterwards
Room temperature, is extracted with water and dichloromethane, then is dried with anhydrous magnesium sulfate, filtering, and removes organic solvent, obtains product crude product；
And post purifying is crossed, obtain the carbazole monomers of R substitutions；
The carbazole monomers that step c replaces above-mentioned R are added to 1,2- dichloros with potassium carbonate, potassium hydroxide and TBAB
In ethane, 5h is reacted under the conditions of 50 DEG C, stand be cooled to room temperature afterwards, extracted with water and dichloromethane, then use anhydrous magnesium sulfate
Dry, filtering, and remove organic solvent, obtain product crude product；And post purifying is crossed, obtain the chloroethyl carbazole monomers of R substitutions；
Chloroethyl carbazole monomers that step d replaces R obtained above and potassium hydroxide, hydroquinones be added to isopropanol and
In the mixed solution of toluene, 3h is reacted under the conditions of 85 DEG C, stand be cooled to room temperature afterwards, solvent is spin-dried for, with water and dichloromethane
Extraction, then dried with anhydrous magnesium sulfate, filtering, and organic solvent is removed, obtain product crude product；And post purifying is crossed, obtain final
Monomer.
4. a kind of application of new bipolar polymer host material as claimed in claim 1, it is characterised in that the material and phosphorus
It is applied in organic electroluminescence device as luminescent layer after the doping of light guest emitting material.Knot in organic electro phosphorescent device
Structure is：Transparent anode/hole transmission layer/polymer host material and phosphorescent guest luminescent material/electron transfer layer/metal are cloudy
Pole, the compound of the material of main part of luminescent layer as described in right 1, guest materials is metal complex phosphor material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710012237.5A CN106854252A (en) | 2017-01-04 | 2017-01-04 | The design synthesis of one class new bipolar polymer host material and its performance study |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710012237.5A CN106854252A (en) | 2017-01-04 | 2017-01-04 | The design synthesis of one class new bipolar polymer host material and its performance study |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106854252A true CN106854252A (en) | 2017-06-16 |
Family
ID=59126619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710012237.5A Pending CN106854252A (en) | 2017-01-04 | 2017-01-04 | The design synthesis of one class new bipolar polymer host material and its performance study |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106854252A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606955A (en) * | 2019-08-12 | 2019-12-24 | 武汉华星光电半导体显示技术有限公司 | Improved hardened layer polymer film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101022156A (en) * | 2007-03-16 | 2007-08-22 | 电子科技大学 | Blue organic electroluminescent device and producing method thereof |
| CN101161692A (en) * | 2007-08-31 | 2008-04-16 | 南京邮电大学 | Rear modified polyvinyl carbazole material and preparation method and uses thereof |
| CN106046054A (en) * | 2016-05-19 | 2016-10-26 | 南京工业大学 | Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods therefor |
-
2017
- 2017-01-04 CN CN201710012237.5A patent/CN106854252A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101022156A (en) * | 2007-03-16 | 2007-08-22 | 电子科技大学 | Blue organic electroluminescent device and producing method thereof |
| CN101161692A (en) * | 2007-08-31 | 2008-04-16 | 南京邮电大学 | Rear modified polyvinyl carbazole material and preparation method and uses thereof |
| CN106046054A (en) * | 2016-05-19 | 2016-10-26 | 南京工业大学 | Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods therefor |
Non-Patent Citations (1)
| Title |
|---|
| SHIYANG SHAO，等: "A Novel, Bipolar Polymeric Host for Highly Efficient Blue Electrophosphorescence: a Non-Conjugated Poly(arylether) Containing Triphenylphosphine Oxide Units in the Electron-Transporting Main Chain and Carbazole Units in Hole-Transporting Side Chains", 《ADVANCED MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606955A (en) * | 2019-08-12 | 2019-12-24 | 武汉华星光电半导体显示技术有限公司 | Improved hardened layer polymer film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101501862B (en) | Polymers with low band gaps and high charge mobility | |
| CN106589324A (en) | Thermal activation delayed fluorescence high-molecular compound and preparation method and application thereof | |
| US10062854B2 (en) | Organic material and photoelectric conversion element | |
| CN101624441A (en) | Preparation method and application method of 4-9, 9-diaryl fluorene polymer material containing substituted radical | |
| CN104981498B (en) | Hyperbranched white-light conjugated polymer and its preparation method and application | |
| CN107118334B (en) | Single white light polymer and electroluminescent organic material and organic electroluminescence device and preparation method thereof | |
| CN1680456B (en) | Electroactive polymer, device made therefrom and method | |
| Coya et al. | Synthesis and tunable emission of novel polyfluorene co-polymers with 1, 8-naphthalimide pendant groups and application in a single layer–single component white emitting device | |
| CN101161698B (en) | Break-in conjugated branched polymer material and preparation method and uses thereof | |
| Xu et al. | Deep-blue emitting poly [spiro (dibenzoazasiline-10′, 9-silafluorene)] for power-efficient PLEDs | |
| CN102167800A (en) | 9-hydroxyl-9'-aromatic conjugate substituted fluorene-containing polymer material and preparation and application methods thereof | |
| CN107955135A (en) | It is conjugated organic grid nanometer polymer and its methods for making and using same | |
| CN106046054A (en) | Vinyl polymer main body material with electron donor-acceptor structure and preparation and application methods therefor | |
| CN108794382A (en) | A kind of multi-functional aggregation-induced emission enhancement compound and the preparation method and application thereof | |
| CN101397365B (en) | 1,8-carbazoles polymer photovoltaic material, preparation and use method thereof | |
| CN109535420A (en) | A kind of dark red smooth high molecular material of thermal activation delayed fluorescence and preparation method thereof | |
| CN106854252A (en) | The design synthesis of one class new bipolar polymer host material and its performance study | |
| Wu et al. | Preparation of a hyperbranched porous polymer and its sensing performance for nitroaromatics | |
| CN100582129C (en) | Rear modified polyvinyl carbazole material and preparation method and uses thereof | |
| CN101503488B (en) | Poly (diaryl fluorene ethylene) material, as well as preparation and use method thereof | |
| CN105669977A (en) | Photoelectric material and preparation method thereof and application to organic electronic device | |
| Li et al. | Near-Infrared (NIR) polymer light-emitting diode (PLED) based on organo-Yb3+-complex-grafted poly (N-vinylcarbazole)(PVK) | |
| CN109593192A (en) | Polyarylether/poly arylidene thio-ester and its preparation method and application with thermal activation delayed fluorescence effect | |
| CN1634927A (en) | Spirofluorene materials containing non-benzene aromatic ring and synthesis and use thereof | |
| Gunning et al. | The development of poly (dendrimer) s for advanced processing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170616 |
|
| WD01 | Invention patent application deemed withdrawn after publication |