KR100295098B1 - Synthetic method of new light-emitting polymers containing oxadiazolse units and el devices using the same - Google Patents
Synthetic method of new light-emitting polymers containing oxadiazolse units and el devices using the same Download PDFInfo
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- KR100295098B1 KR100295098B1 KR1019980043226A KR19980043226A KR100295098B1 KR 100295098 B1 KR100295098 B1 KR 100295098B1 KR 1019980043226 A KR1019980043226 A KR 1019980043226A KR 19980043226 A KR19980043226 A KR 19980043226A KR 100295098 B1 KR100295098 B1 KR 100295098B1
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- Prior art keywords
- oxadiazole
- bis
- hydrogen
- linear
- alkyl group
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 238000010189 synthetic method Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- -1 oxadiazole compound Chemical class 0.000 claims description 18
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 16
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- XFNNAMBYJSQXKF-UHFFFAOYSA-N 3-methylbenzohydrazide Chemical compound CC1=CC=CC(C(=O)NN)=C1 XFNNAMBYJSQXKF-UHFFFAOYSA-N 0.000 claims description 6
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- AUZMNYKPHNABDE-UHFFFAOYSA-N 2,5-bis[3-(bromomethyl)phenyl]-1,3,4-oxadiazole Chemical compound BrCC1=CC=CC(C=2OC(=NN=2)C=2C=C(CBr)C=CC=2)=C1 AUZMNYKPHNABDE-UHFFFAOYSA-N 0.000 claims description 5
- WOOBPQAPKPZXLS-UHFFFAOYSA-N 2,5-bis[4-(bromomethyl)phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(CBr)=CC=C1C1=NN=C(C=2C=CC(CBr)=CC=2)O1 WOOBPQAPKPZXLS-UHFFFAOYSA-N 0.000 claims description 5
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 5
- XYCVDMCFWPHYNZ-UHFFFAOYSA-N 2,5-bis(4-methylphenyl)-1,3,4-oxadiazole Chemical compound C1=CC(C)=CC=C1C1=NN=C(C=2C=CC(C)=CC=2)O1 XYCVDMCFWPHYNZ-UHFFFAOYSA-N 0.000 claims description 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 claims description 3
- OHWQVYVPAAGBHW-UHFFFAOYSA-N 2,5-bis(3-methylphenyl)-1,3,4-oxadiazole Chemical compound CC1=CC=CC(C=2OC(=NN=2)C=2C=C(C)C=CC=2)=C1 OHWQVYVPAAGBHW-UHFFFAOYSA-N 0.000 claims description 3
- GPSDUZXPYCFOSQ-UHFFFAOYSA-M m-toluate Chemical compound CC1=CC=CC(C([O-])=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical compound CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 claims 2
- GPTOGZLZMLJZCV-UHFFFAOYSA-N (3-methylphenyl)hydrazine Chemical compound CC1=CC=CC(NN)=C1 GPTOGZLZMLJZCV-UHFFFAOYSA-N 0.000 claims 1
- KPXPOQZREGLITO-UHFFFAOYSA-N 2-[3-(bromomethyl)phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(=CC(=C1)C2=NN=CO2)CBr KPXPOQZREGLITO-UHFFFAOYSA-N 0.000 claims 1
- KICJLCKEMVHVIR-UHFFFAOYSA-N NN.C1(=CC=C(C=C1)C(=O)O)C Chemical compound NN.C1(=CC=C(C=C1)C(=O)O)C KICJLCKEMVHVIR-UHFFFAOYSA-N 0.000 claims 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000002347 injection Methods 0.000 abstract description 10
- 239000007924 injection Substances 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 150000004866 oxadiazoles Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 239000007787 solid Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- MCQJGNPLAHIBPZ-UHFFFAOYSA-N 1,2-bis(3-methylphenyl)hydrazine Chemical compound CC1=CC=CC(NNC=2C=C(C)C=CC=2)=C1 MCQJGNPLAHIBPZ-UHFFFAOYSA-N 0.000 description 4
- MFFVZXOPRXMVET-UHFFFAOYSA-N 4-methylbenzohydrazide Chemical compound CC1=CC=C(C(=O)NN)C=C1 MFFVZXOPRXMVET-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical class CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- AMRKNJUDRORQMI-UHFFFAOYSA-N 1,2-bis(4-methylphenyl)hydrazine Chemical compound C1=CC(C)=CC=C1NNC1=CC=C(C)C=C1 AMRKNJUDRORQMI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 238000007239 Wittig reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-M p-toluate Chemical compound CC1=CC=C(C([O-])=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-M 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- DCJKUXYSYJBBRD-UHFFFAOYSA-N 2,5-diphenyl-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C=CC=CC=2)O1 DCJKUXYSYJBBRD-UHFFFAOYSA-N 0.000 description 1
- UORXCQDFXKKDOV-UHFFFAOYSA-N 2-(2-ethylhexoxy)-5-methoxyterephthalaldehyde Chemical compound CCCCC(CC)COC1=CC(C=O)=C(OC)C=C1C=O UORXCQDFXKKDOV-UHFFFAOYSA-N 0.000 description 1
- IUKXRBAYNRAFFQ-UHFFFAOYSA-N 2-(3-methylphenyl)-1,3,4-oxadiazole Chemical compound CC1=CC=CC(C=2OC=NN=2)=C1 IUKXRBAYNRAFFQ-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
본 발명은 발광 고분자에서 전자의 주입과 수송 능력을 우수하게 하는 구조식 (M-1) 및 (M-2)의 옥사디아졸 유도체를 얻고, 이를 정공 수송 능력이 우수한 화합물과 반응시켜 유기용매에 용해 가능하며, 전자와 정공 수송 능력이 우수한 일반식(P-1 ∼ P-2)의 발광 고분자를 합성하고, 이를 이용한 전기 발광 소자에 관한 것으로, 한 고분자 사슬 내에 전자와 정공 수송 능력이 우수한 반복 단위가 함께 있도록 하여 전자와 정공의 주입을 용이하게 하고 여기자의 생성 확률을 높여 전기 발광 소자의 발광 효율을 크게 향상시켰다.The present invention provides oxadiazole derivatives of the structural formulas (M-1) and (M-2) which excel in the injection and transporting ability of electrons in a light emitting polymer and are reacted with a compound having excellent hole transporting ability to dissolve in an organic solvent (P-1 to P-2), which is excellent in electron and hole transportability, and relates to an electroluminescent device using the same. In a polymer chain, Thereby facilitating the injection of electrons and holes and increasing the probability of formation of excitons, thereby greatly improving the luminous efficiency of the electroluminescent device.
Description
본 발명은 발광 고분자 합성용의 신규한 옥사디아졸 및 신규한 발광 고분자 합성 방법과 이를 이용한 전기 발광 소자에 관한 것으로서, 좀 더 구체적으로는 발광 고분자에서 전자의 주입과 수송 능력을 우수하게 하는 하기 구조식 (M-1) 및 (M-2)의 옥사디아졸 유도체를 얻고, 이를 정공 수송 능력이 우수한 화합물과 반응시켜 유기용매에 용해 가능하며, 전자와 정공 수송 능력이 우수한 하기 일반식(P-1 ∼ P-2)의 발광 고분자를 합성하고, 이를 이용한 전기 발광 소자에 관한 것이다.The present invention relates to a novel oxadiazole and a novel electroluminescent polymer synthesizing method for synthesizing a light emitting polymer and an electroluminescent device using the same. More particularly, the present invention relates to a novel electroluminescent device, (P-1) and (M-2) which are excellent in electron and hole transporting ability and can be dissolved in an organic solvent by reacting them with a compound having excellent hole transporting ability, To P-2), and to an electroluminescent device using the polymer.
또는or
이고, R1,R4,R5,R6및 R7은 수소 또는 C1∼C29의 선형 또는 분지형 알킬기이며, R2및 R3는 수소 또는 C1∼C20의 선형 또는 분지형 알킬기 또는 알콕시기이다. And, R 1, R 4, R 5, R 6 and R 7 is a linear or branched alkyl group of hydrogen or C 1 ~C 29, R 2 and R 3 are hydrogen or linear or branched C 1 ~C 20 An alkyl group or an alkoxy group.
지금까지 고분자 전기 발광 소자의 발광 재료로 가장 많이 사용되고 있는 발광 물질로는 폴리(1,4-페닐렌비닐렌) (PPV), 폴리파라페닐렌 (PPP), 폴리티오펜 (PT)과 같은 π-공액 고분자가 가장 일반적이다. 이러한 π-공액 고분자는 양극으로부터 정공의 주입과 주입된 정공의 수송 능력은 우수하나 음극으로부터 전자의 주입과 수송 능력은 좋지 못하여, 양극으로부터 주입된 정공이 전자와 채 결합되기 전에 음극으로 흘러가게 되어 전자와 정공의 결합 확률이 떨어져 제작된 전기 발광 소자의 발광 효율이 낮은 단점이 있었다.Until now, the luminescent materials most widely used as the light emitting material of the polymer electroluminescent devices include poly (1,4-phenylene vinylene) (PPV), polyparaphenylene (PPP), polythiophene - Conjugated polymers are the most common. This π-conjugated polymer has excellent ability to inject holes from the anode and transport the injected holes, but the injection and transporting ability of the electrons from the cathode is not good, and the holes injected from the anode flow to the cathode before they are bonded to the electrons There is a disadvantage in that the electroluminescence device manufactured has a low luminous efficiency because the probability of coupling of electrons and holes is low.
특히, 미국 특허 제5,247,190호에는 전도성 고분자로 알려진 폴리(1,4-페닐렌비닐렌)과 그 유도체들이 발광물질로 사용함을 기재하고 있고, 미국 특허제5,514,878호에는 높은 전자친화도를 가지는 CN기를 포함하는 발광고분자를 사용하여 금속 전극으로부터 전자의 주입을 용이하게 하고 전자와 정공의 결합확율을 높여 발광소자의 효율을 향상시키는 방법이 기재되어 있으며, 미국 특허 제5,376,456호에는 페닐렌 비닐렌 단위와 삼불화 메틸기가 치환된 두 개의 벤젠기를 포함하고 있는 단위의 공중합체가 기재되어 있지만 대체적으로 음극으로부터 전자의 주입과 수송 능력은 좋지 못하여, 양극으로부터 주입된 정공이 전자와 채 결합되기 전에 음극으로 흘러가게 되어 전자와 정공의 결합 확률이 떨어져 제작된 전기 발광 소자의 발광 효율이 만족스럽지 못하였다.In particular, U.S. Patent No. 5,247,190 discloses that poly (1,4-phenylenevinylene) and derivatives thereof, which are known as conductive polymers, are used as light emitting materials, and U.S. Patent No. 5,514,878 discloses a CN group having high electron affinity Discloses a method of facilitating the injection of electrons from a metal electrode and improving the efficiency of a light emitting device by increasing the probability of bonding of electrons and holes using a light emitting polymer, and U.S. Patent No. 5,376,456 discloses a method of improving the efficiency of a light emitting device, A copolymer containing two benzene groups substituted with a trifluoromethyl group is described. However, since the injection and transporting ability of electrons from the cathode is generally poor, the holes injected from the anode flow into the cathode before being bonded to the electrons The probability of coupling of electrons and holes is low and the luminous efficiency of the manufactured electroluminescent device is not satisfactory The.
따라서, 본 발명의 목적은 전자 주입과 수송 능력이 우수한 발광 고분자 합성용 신규한 옥사디아졸 화합물과 이의 합성 방법을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a novel oxadiazole compound for synthesizing a light emitting polymer having excellent electron injection and transporting ability and a method for synthesizing the same.
본 발명의 다른 목적은 상기 목적의 옥사디아졸 화합물을 전자 주입과 수송 능력이 우수한 반복 단위로 하고 정공 수송 능력이 우수한 반복 단위가 교대로 연결된 신규한 발광 고분자 및 이의 합성 방법을 제공하는 데 있다.Another object of the present invention is to provide a novel light emitting polymer in which the above-mentioned oxadiazole compound is alternately connected with repeating units having excellent electron injection and transportability and excellent hole transportability, and a method for synthesizing the same.
본 발명의 또 다른 목적은 상기 목적의 발광 고분자를 발광층으로 하는 전기 발광 소자를 제공하는 데 있다.It is still another object of the present invention to provide an electroluminescent device using the above-described light emitting polymer as a light emitting layer.
상기 목적들 뿐만 아니라 용이하게 표출될 수 있는 또 다른 목적을 달성하기 위하여 본 발명에서는 한 고분자 사슬 내에 전자와 정공 수송 능력이 우수한 반복 단위가 함께 있도록 하여 전자와 정공의 주입을 용이하게 하고 여기자의 생성 확률을 높여 전기 발광 소자의 발광 효율을 크게 향상시켰다.In order to achieve the above-mentioned objects as well as another object which can be easily expressed, in the present invention, it is possible to facilitate the injection of electrons and holes by making repetitive units having excellent electron and hole transporting ability together in one polymer chain, Thereby improving the luminous efficiency of the electroluminescent device.
도 1 은 본 발명에 따른 전기 발광 소자의 단면도.1 is a cross-sectional view of an electroluminescent device according to the present invention.
도 2 는 실시예 11 ∼ 14에 의해 합성된 발광 고분자들의 UV 흡수 스펙트럼을 도시한 그래프.2 is a graph showing UV absorption spectra of the light emitting polymers synthesized by Examples 11 to 14. Fig.
도 3 은 실시예 11 ∼ 14에 의해 합성된 발광 고분자들의 PL 발광 스펙트럼을 도시한 그래프.FIG. 3 is a graph showing PL emission spectra of the light emitting polymers synthesized by Examples 11 to 14. FIG.
도 4 는 실시예 11에 의해 합성된 고분자를 이용한 단일층 발광 소자의 전류-전압 특성을 도시한 그래프.FIG. 4 is a graph showing current-voltage characteristics of a single-layered light-emitting device using the polymer synthesized in Example 11. FIG.
도 5 는 실시예 11에 의해 합성된 고분자를 이용한 단일층 발광 소자의 전압-발광 세기 특성을 도시한 그래프.5 is a graph showing voltage-luminescence intensity characteristics of a single-layered light-emitting device using the polymer synthesized in Example 11. Fig.
* 도면의 주요 부분에 대한 부호 설명 *Description of the Related Art [0002]
1: 기판 2: 반투명 전극1: substrate 2: translucent electrode
3: 정공 수송층 4: 고분자 발광 층3: hole transport layer 4: polymer light emitting layer
5: 전자 수송층 6: 금속 전극5: electron transport layer 6: metal electrode
본 발명에 따른 전자 주입과 수송 능력이 우수한 발광 고분자 합성용 신규한 옥사디아졸 화합물은 하기 구조식 (M-1) 및 (M-2)로 표현되며, 신규한 발광 고분자는 하기 일반식(P-1 ∼ P-2)로 표현된다.The novel oxadiazole compound for synthesis of a light emitting polymer having excellent electron injection and transport ability according to the present invention is represented by the following structural formulas (M-1) and (M-2) 1 to P-2).
또는or
이고, R1,R4,R5,R6및 R7은 수소 또는 C1∼C29의 선형 또는 분지형 알킬기이며, R2및 R3는 수소 또는 C1∼C20의 선형 또는 분지형 알킬기 또는 알콕시기이다. And, R 1, R 4, R 5, R 6 and R 7 is a linear or branched alkyl group of hydrogen or C 1 ~C 29, R 2 and R 3 are hydrogen or linear or branched C 1 ~C 20 An alkyl group or an alkoxy group.
즉, 수송 능력이 우수한 반복 단위로는 오르소 (ortho) 혹은 메타(meta)로 연결된 옥사디아졸(oxadiazole)을 선택하였고, 정공 수송 능력이 우수한 반복 단위로는 카바졸(carbazole), 페닐(phenyl), 플루오렌(fluorene), 티오펜(thiophene)을 선택하였다. 두 반복 단위의 연결은 위티그(Wittig) 반응이나 위티그-에몬스(Wittig-Emons) 반응을 이용하여 고분자 전체가 π-공액화 되도록 비닐기로 연결하였다. 두 반복 단위를 고분자화 하기 위하여 옥사디아졸 단위는 두 개의 포스포니움 염(phosphonium salt)이나 포스포네이트(phosphonate)를 도입하였고, 정공 수송을 위한 카바졸, 페닐, 플루오렌, 티오펜에는 두 개의 알데히드 기를 도입하였다.That is, oxadiazole connected with ortho or meta was selected as a repeating unit having excellent transportability, and repeating units having excellent hole transportability include carbazole, phenyl (phenyl ), Fluorene, and thiophene were selected. The linking of the two repeating units was carried out by a vinyl group such that the entire polymer was conjugated by using a Wittig reaction or a Wittig-Emons reaction. In order to polymerize two repeating units, two phosphonium salts or phosphonates were introduced into the oxadiazole unit, and two carbazole, phenyl, fluorene and thiophenes were used for hole transport Aldehyde groups were introduced.
본 발명에 따른 전기 발광 소자 및 이의 제조 방법은 기판 상부에 투명한 전극, 정공 수송층, 고분자 발광층, 전자 수송층 및 금속 전극을 순차적으로 형성하되, 상기 고분자 발광층은 전자 수송 능력이 우수한 상기 구조식 (M-1) 및 (M-2)로 표현되는 옥시디아졸과, 정공 수송 능력이 우수한 카바졸, 페닐, 플루오렌 혹은 티오펜이 이중 결합으로 연결된 고분자로 형성되는 것을 특징으로 한다.The electroluminescent device and the method of fabricating the same according to the present invention are characterized by sequentially forming a transparent electrode, a hole transport layer, a polymer luminescent layer, an electron transport layer and a metal electrode on a substrate, wherein the polymer luminescent layer has a structure represented by the structural formula ) And (M-2), and a polymer having a carbazole, phenyl, fluorene or thiophene, which is excellent in hole transporting ability, and connected by a double bond.
먼저, 화학식 17과 같이 4-메틸벤조에이트와 히드라진을 반응시켜 4-메틸벤조산 히드라지드를 수득하고, 상기 4-메틸벤조산 히드라지드를 p-톨루일클로라이드와 반응시켜 비스(4-메틸페닐)히드라진을 수득한 후, 상기 비스(4-메틸페닐)히드라진을 포스포릴 클로라이드와 반응시켜 2,5-비스[4-메틸페닐]-1,3,4-옥사디아졸을 수득한 다음, 상기 2,5-비스[4-메틸페닐]-1,3,4-옥사디아졸을 N-브로모숙신이미드와 반응시켜 2,5-비스[4-(브로모메틸)페닐]-1,3,4-옥사디아졸을 수득하고, 상기 2,5-비스[4-(브로모메틸)페닐]-1,3,4-옥사디아졸을 트리페닐포스핀과 반응시켜 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸을 수득한다.First, 4-methylbenzoic acid hydrazide is obtained by reacting 4-methylbenzoate with hydrazine as shown in Chemical Formula 17, and the 4-methylbenzoic acid hydrazide is reacted with p-toluyl chloride to obtain bis (4-methylphenyl) hydrazine Bis (4-methylphenyl) -1,3,4-oxadiazole was obtained by reacting the bis (4-methylphenyl) hydrazine with phosphoryl chloride to obtain 2,5-bis [4-methylphenyl] -1,3,4-oxadiazole was reacted with N-bromosuccinimide to give 2,5-bis [4- (bromomethyl) phenyl] -1,3,4-oxadiazole Bis (4-tolylene-phenyl) -1,3,4-oxadiazole was reacted with triphenylphosphine to obtain 2,5-bis [4- Triphenylphosphonium < / RTI > bromide) -1,3,4-oxadiazole.
이를 반응 도식으로 표현하면 다음과 같다.The reaction scheme is as follows.
또한, 화학식 18과 같이 3-메틸벤조에이트와 히드라진을 반응시켜 3-메틸벤조산 히드라지드를 수득하고, 상기 3-메틸벤조산 히드라지드를 p-톨루일클로라이드와 반응시켜 비스(3-메틸페닐)히드라진을 수득한 후, 상기 비스(3-메틸페닐)히드라진을 포스포릴 클로라이드와 반응시켜 2,5-비스[3-메틸페닐]-1,3,4-옥사디아졸을 수득한 다음, 상기 2,5-비스[3-메틸페닐]-1,3,4-옥사디아졸을 N-브로모숙신이미드와 반응시켜 2,5-비스[3-(브로모메틸)페닐]-1,3,4-옥사디아졸을 수득하고, 상기 2,5-비스[3-(브로모메틸)페닐]-1,3,4-옥사디아졸을 트리페닐포스핀과 반응시켜 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸을 수득한다.Also, 3-methylbenzoic acid hydrazide is obtained by reacting 3-methylbenzoate with hydrazine as shown in Formula 18, and the 3-methylbenzoic acid hydrazide is reacted with p-toluyl chloride to obtain bis (3-methylphenyl) hydrazine The obtained bis (3-methylphenyl) hydrazine is reacted with phosphoryl chloride to obtain 2,5-bis [3-methylphenyl] -1,3,4-oxadiazole, [3-methylphenyl] -1,3,4-oxadiazole was reacted with N-bromosuccinimide to give 2,5-bis [3- (bromomethyl) phenyl] -1,3,4-oxadiazole (2,5-bis [3- (bromomethyl) phenyl] -1,3,4-oxadiazole is reacted with triphenylphosphine to obtain 2,5-bis Triphenylphosphonium < / RTI > bromide) -1,3,4-oxadiazole.
그 다음에 상기 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸 또는 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸을 정공 수송 능력이 우수한 카바졸(carbazole), 페닐(phenyl),플루오렌(fluorene), 티오펜(thiophene) 반복 단위와 위티그(Wittig)반응 또는 위티그-에몬스(Wittig-Emons)반응시켜 본 발명의 발광 고분자를 얻는다.(4-tolylene-triphenylphosphonium bromide) -1,3,4-oxadiazole or 2,5-bis (3-toylene-triphenylphosphonium bromide) ) -1,3,4-oxadiazole is reacted with carbazole, phenyl, fluorene, thiophene repeating units and Wittig reaction, which have excellent hole transporting ability, Tg-Emmons (Wittig-Emons) to obtain a light-emitting polymer of the present invention.
즉, 상기 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸 또는 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸과 일반식 (11)로 표현되는 디알데히드 단량체를 반응시켜 일반식 (P-1)과 (P-2)로 표현되는 발광 고분자를 얻는다.That is, the above 2,5-bis (4-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole or 2,5-bis (3-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole is reacted with a dialdehyde monomer represented by the general formula (11) to obtain a light emitting polymer represented by the general formulas (P-1) and (P-2).
여기서, Ar은Here, Ar
또는or
이고, R1,R4, R5, R6및 R7은 수소 또는 C1∼ C29의 선형 또는 분지형 알킬기이며, R2및 R3는 수소 또는 C1∼ C20의 선형 또는 분지형 알킬기 또는 알콕시기이다. And, R 1, R 4, R 5, R 6 and R 7 is a linear or branched alkyl group of hydrogen or C 1 ~ C 29, R 2 and R 3 are hydrogen or C 1 ~ C 20 linear or branched, An alkyl group or an alkoxy group.
특히, 상기 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸을 3,6-디포밀-9-(2-에틸헥실)-카바졸(화학식 M-3)과 위티그(Wittig) 반응을 통하여 폴리[(2,5-디페닐-1,3,4-옥시디아졸)-4-디일비닐렌-교대-3,6-(9-(2-에틸헥실)-카바졸렌비닐렌)](P-3화합물)을 수득하며, 상기 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸을 3,6-디포밀-9-(2-에틸헥실)-카바졸(화학식 M-3)과 위티그(Wittig) 반응을 통하여 폴리[(2,5-디페닐-1,3,4-옥시디아졸)-3-디일비닐렌-교대-3,6-(9-(2-에틸헥실)-카바졸렌비닐렌)](P-4화합물)을 수득하고, 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸(화학식 M-1)을(2-메톡시-5-(2'-에틸헥실옥시))테레프탈알데히드(화학식 M-4)과 위티그(Wittig) 반응을 통하여 폴리[(2,5-디페닐-1,3,4-옥시디아졸)-4-디일비닐렌-교대-(2-메톡시-5-(2'-에틸헥실옥시)-1,4-페닐렌비닐렌)](P-5화합물)을 수득하며, 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸(화학식 M-2)을(2-메톡시-5-(2'-에틸헥실옥시))테레프탈알데히드(화학식 M-4)과 위티그(Wittig) 반응을 통하여 폴리[(2,5-디페닐-1,3,4-옥시디아졸)-3-디일비닐렌-교대-(2-메톡시-5-(2'-에틸헥실옥시)-1,4-페닐렌비닐렌)](P-6화합물)을 수득한다.In particular, the 2,5-bis (4-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole is reacted with 3,6-DOPOHMYL-9- (2-ethylhexyl) (2,5-diphenyl-1,3,4-oxydiazole) -4-diylvinylene-alternan-3,6- (9- (3-tolylene-triphenylphosphonium bromide) -1,3,4-triazol-3-yl) - (2-ethylhexyl) (2,5-diphenyl-1,3-dioxolan-2-yl) -oxadiazole was obtained through 3,6-diphomyl-9- 3-diylvinylene-alternan-3,6- (9- (2-ethylhexyl) -carbazolenevinylene)] (P-4 compound) Bis (4-tolylene-triphenylphosphonium bromide) -1,3,4-oxadiazole (M-1) is reacted with (2-methoxy-5- (2'-ethylhexyloxy)) terephthalate aldehyde (formula M-4) with Wittig (Wittig) through the reaction poly [(2,5-diphenyl-1,3,4-oxadiazole) diyl-4-vinylene-T - (2-methoxy-5- (2'-ethylhexyloxy) -1,4-phenylenevinylene)] (P-5 compound) 4-oxadiazole (Formula M-2) is reacted with (2-methoxy-5- (2'-ethylhexyloxy)) terephthalaldehyde (M- (2,5-diphenyl-1,3,4-oxydiazole) -3-diylvinylene-alterna- (2-methoxy-5- (2 & Ethylhexyloxy) -1,4-phenylenevinylene)] (P-6 compound).
이를 반응 도식으로 표현하면 다음과 같다.The reaction scheme is as follows.
한편, 상기 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸 또는 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸 대신에 하기 구조식 (M-5) 또는 (M-6)로 표현되는 포스포네이트구조체를 가지는 단량체와 상기 일반식 (11)로 표현되는 디알데히드 단량체를 반응시켜 일반식 (P-1) 또는 (P-2)로 표현되는 발광 고분자를 얻을 수도 있다.On the other hand, the above 2,5-bis (4-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole or 2,5-bis (3-toylene-triphenylphosphonium bromide) A monomer having a phosphonate structure represented by the following structural formula (M-5) or (M-6) is reacted with a dialdehyde monomer represented by the above general formula (11) in place of -1,3,4- To obtain a light emitting polymer represented by the general formula (P-1) or (P-2).
상기 식에서 Ar은 상기 화학식 19에서 설명한 바와 같다.In the above formula, Ar is as described in the above formula (19).
다음의 실시예는 본 발명을 좀 더 상세히 설명하는 것이지만, 본 발명의 범주를 한정하는 것은 아니다.The following examples illustrate the invention in more detail but do not limit the scope of the invention.
실시예 1 : 4-메틸벤조산 히드라지드의 합성Example 1: Synthesis of 4-methylbenzoic acid hydrazide
20 g (130 mmol)의 4-메틸벤조에이트 (화학식 1)과 과량의 유수 히드라진을 100 mL의 메탄올에 용해한 후, 80℃에서 30 시간 동안 반응시킨다. 반응이 끝난 후, 물과 에틸 아세테이트를 이용하여 반응 용액을 추출한다. 에틸 아세테이트 층을 분리한 후, 황산마그네슘으로 물을 제거하고, 용매를 로터리 증류기로 제거한 다음, 진공하에서 건조하여 18.6 g의 흰색 고체를 얻는다.20 g (130 mmol) of 4-methylbenzoate (Formula 1) and excess hydrazine hydrate were dissolved in 100 mL of methanol, and the mixture was reacted at 80 ° C. for 30 hours. After the reaction is completed, the reaction solution is extracted with water and ethyl acetate. The ethyl acetate layer was separated, the water was removed with magnesium sulfate, the solvent was removed with a rotary distiller, and then dried under vacuum to obtain 18.6 g of a white solid.
수득율: 93 %.Yield: 93%.
녹는점: 121-123℃.Melting point: 121-123 ℃.
1H-NMR (CDCl3, ppm): ( 9.9 (s, 1H), 7.6 (d, 2H), 7.1 (d, 2H), 4.6 (s, 2H), 2.3 (s, 3H).1H NMR (CDCl3, ppm): 9.9 (s, IH), 7.6 (d, 2H), 7.1 (d, 2H), 4.6 (s, 2H), 2.3 (s, 3H).
원소분석 [분석치: C, 63.76; H, 6.66; N, 18.59. 이론치: C, 63.98; H, 6.71; N, 18.65.]Elemental analysis [Anal. C, 63.76; H, 6.66; N, 18.59. Theoretical values: C, 63.98; H, 6.71; N, 18.65.]
실시예 2 : 비스(4-메틸페닐) 히드라진의 합성Example 2: Synthesis of bis (4-methylphenyl) hydrazine
6 g의 4-메틸벤조산 히드라지드 (40 mmol)과 p-톨루일 클로라이드 (40 mmol)을 30 mL의 N,N-디메틸아세트아미드 용액에 녹인다. 0℃에서 세 시간 반응 시킨 후, 5 mL의 피리딘을 가한다. 반응 용액을 0℃의 찬물에 부어 침전 시킨다. 침전물을 필터하여 얻은 다음, 진공 오븐에서 건조한다. 건조한 침전물을 메탄올에서 재결정하여 9.5 g 흰색의 깨끗한 고체를 얻는다.6 g of 4-methylbenzoic acid hydrazide (40 mmol) and p-toluyl chloride (40 mmol) are dissolved in 30 mL of N, N-dimethylacetamide solution. After three hours of reaction at 0 ° C, 5 mL of pyridine is added. The reaction solution is poured into cold water at 0 캜 to precipitate. The precipitate is filtered off and then dried in a vacuum oven. The dry precipitate is recrystallized from methanol to give 9.5 g of a white, clear solid.
수득율: 89 %.Yield: 89%.
녹는점: 257-258℃.Melting point: 257-258 ℃.
1H-NMR (DMSO, ppm): ( 10.4 (s, 2H), 7.8 (d, 4H), 7.3 (d, 4H), 2.3 (s, 6H).1 H-NMR (DMSO, ppm): (10.4 (s, 2H), 7.8 (d, 4H), 7.3 (d, 4H), 2.3 (s, 6H).
원소분석 [분석치: C, 71.29; H, 5.99; N, 10.44. 이론치: C, 71.62; H, 6.01; N, 10.44.]Elemental analysis [Anal. C, 71.29; H, 5.99; N, 10.44. Theoretical values: C, 71.62; H, 6.01; N, 10.44.]
실시예 3 : 2,5-비스(4-메틸페닐)-1,3,4-옥시디아졸의 합성.Example 3: Synthesis of 2,5-bis (4-methylphenyl) -1,3,4-oxadiazole.
5 g의 비스(4-메틸페닐) 히드라진 (19 mmol)과 50 mL의 포스포릴 클로라이드를 80℃에서 16시간 반응시킨다. 반응 후 남아 있는 포스포릴 클로라이드를 반응 용액으로부터 증류하여 제거한 다음, 물과 염화 메틸렌으로 추출한다. 염화 메틸렌 층을 분리하여 황산마그네슘으로 물을 제거한 다음, 용매를 로터리 증류기로 제거하고 남은 고체 화합물을 진공하에서 건조한다. 얻은 고체 화합물을 메탄올 용액에서 재결정하여 4.0 g의 깨끗한 고체 화합물을 얻는다.5 g of bis (4-methylphenyl) hydrazine (19 mmol) and 50 mL of phosphoryl chloride are reacted at 80 DEG C for 16 hours. After the reaction, the remaining phosphoryl chloride is distilled off from the reaction solution and extracted with water and methylene chloride. The methylene chloride layer is separated, water is removed with magnesium sulfate, the solvent is removed with a rotary distiller, and the remaining solid compound is dried under vacuum. The obtained solid compound was recrystallized in methanol solution to obtain 4.0 g of a clean solid compound.
수득율: 85 %.Yield: 85%.
녹는점: 164-166℃.Melting point: 164-166 ° C.
1H-NMR (CDCl3, ppm): ( 8.0 (d, 4H), 7.3 (d, 4H), 2.4 (s, 6H).1 H-NMR (CDCl 3, ppm): (8.0 (d, 4H), 7.3 (d, 4H), 2.4 (s, 6H).
원소분석 [분석치: C, 76.34; H, 5.64; N, 11.34. 이론치: C, 76.78; H, 5.64; N, 11.19.]Elemental analysis [Anal. C, 76.34; H, 5.64; N, 11.34. Theoretical values: C, 76.78; H, 5.64; N, 11.19.]
실시예 4 : 2,5-비스[4-(브로모메틸)페닐]-1,3,4-옥시디아졸의 합성.Example 4: Synthesis of 2,5-bis [4- (bromomethyl) phenyl] -1,3,4-oxadiazole.
3.6 g의 2,5-비스(4-메틸페닐)-1,3,4-옥시디아졸(14 mmol)과 5.5 g의 N-브로모숙신이미드(28 mmol) 및 소량의 과산화 벤조산을 100 mL의 사염화탄소에 가한 후 5시간 동안 환류하였다. 반응 후 반응 용기 표면에 뜨는 숙신 이미드를 필터하여 제거하고 용매를 로터리 증류기로 제거한다. 생성된 고체 화합물을 메탄올에 씻어서 필터한 후 진공 오븐에서 건조 하여 4.3 g의 흰색 고체를 얻는다.A mixture of 3.6 g of 2,5-bis (4-methylphenyl) -1,3,4-oxadiazole (14 mmol), 5.5 g of N-bromosuccinimide (28 mmol) and a small amount of benzoyl peroxide Of carbon tetrachloride and refluxed for 5 hours. After the reaction, the succinimide floating on the surface of the reaction vessel is filtered out, and the solvent is removed by rotary distillation. The resulting solid compound is washed in methanol, filtered and dried in a vacuum oven to obtain 4.3 g of a white solid.
수득율: 75 %.Yield: 75%.
녹는점: 224-225℃.Melting point: 224-225 ℃.
1H-NMR (CDCl3, ppm): ( 8.1 (d, 4H), 7.5 (d, 4H), 4.5 (s, 4H).1 H-NMR (CDCl 3, ppm): (8.1 (d, 4H), 7.5 (d, 4H), 4.5 (s, 4H).
원소분석 [분석치: C, 47.37; H, 3.09; N, 7.02. 이론치: C, 47.09; H, 2.96; N, 6.86.]Elemental analysis [Analytical value: C, 47.37; H, 3.09; N, 7.02. Theoretical values: C, 47.09; H, 2.96; N, 6.86.]
실시예 5 : 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥시디아졸의 합성.Example 5: Synthesis of 2,5-bis (4-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole.
3.0 g(7.0 mmol)의 2,5-비스[4-(브로모메틸)페닐]-1,3,4-옥시디아졸과 4.3 g(16 mmol)의 트리페닐 포스핀을 30 mL의 디메틸포름이미드 (DMF) 용액에 녹인 후 24 시간 환류하였다. 반응 후 용액을 과량의 디에틸 에테르에 부어 침전 시켰다. 침전물을 디에틸 에테르로 여러 번 씻어준 다음 필터하여 진공 오븐에서 건조하여 4.6 g의 흰색 고체를 얻는다.4.3 g (16 mmol) of triphenylphosphine and 3.0 g (7.0 mmol) of 2,5-bis [4- (bromomethyl) phenyl] -1,3,4-oxadiazole were dissolved in 30 mL of dimethyl form Imide (DMF) solution and refluxed for 24 hours. After the reaction, the solution was poured into excess diethyl ether to precipitate. The precipitate is washed several times with diethyl ether, filtered and dried in a vacuum oven to give 4.6 g of a white solid.
수득율: 82%.Yield: 82%.
녹는점: 240-241℃.Melting point: 240-241 ℃.
1H-NMR (CDCl3, ppm): ( 7.8-7.5 (m, 34H), 7.1 (d, 4H), 5.1 (d, 4H).원소분석 [분석치: C, 66.88; H, 4.55; N, 3.12. 이론치: C, 66.97; H, 4.54; N, 3.00.]1 H-NMR (CDCl 3, ppm): (7.8-7.5 (m, 34H), 7.1 (d, 4H), 5.1 (d, 4H). Elemental analysis. Anal. C, 66.88; H, 4.55; Theoretical: C, 66.97; H, 4.54; N, 3.00.]
실시예 6 : 3-메틸벤조산 히드라지드의 합성.Example 6: Synthesis of 3-methylbenzoic acid hydrazide.
20 g(133 mmol)의 3-메틸벤조에이트(화학식 1)과 과량의 유수 히드라지드를 100 mL의 메탄올에 녹인 후, 80℃에서 30시간 동안 반응시킨다. 반응이 끝난 후, 물과 에틸 아세테이트를 이용하여 반응 용액을 추출한다. 에틸 아세테이트 층을 분리한 후 황산마그네슘으로 물을 제거하고, 용매를 로터리 증류기로 제거한 다음 진공하에서 건조하여 19.0 g의 흰색 고체를 얻는다.20 g (133 mmol) of 3-methylbenzoate (Formula 1) and an excess amount of hydrazide hydrate were dissolved in 100 mL of methanol, and the mixture was reacted at 80 ° C. for 30 hours. After the reaction is completed, the reaction solution is extracted with water and ethyl acetate. The ethyl acetate layer was separated, the water was removed with magnesium sulfate, the solvent was removed with a rotary distiller, and then dried under vacuum to obtain 19.0 g of a white solid.
수득율: 95 %.Yield: 95%.
녹는점: 100-101℃.Melting point: 100-101 ℃.
1H-NMR (CDCl3, ppm): ( 9.5 (s, 1H), 7.5 (m, 2H), 7.2 (m, 2H), 5.4 (s, 2H), 2.3 (s, 3H).1H NMR (CDCl3, ppm): (9.5 (s, 1H), 7.5 (m, 2H), 7.2 (m, 2H), 5.4 (s, 2H), 2.3 (s,
원소분석 [분석치: C, 63.68; H, 6.61; N, 18.61. 이론치: C, 63.98; H, 6.71; N, 18.65]Elemental analysis [Anal. C, 63.68; H, 6.61; N, 18.61. Theoretical values: C, 63.98; H, 6.71; N, 18.65]
실시예 7 : 비스(3-메틸페닐) 히드라진의 합성.Example 7: Synthesis of bis (3-methylphenyl) hydrazine.
6 g의 3-메틸벤조산 히드라지드(40 mmol)과 p-톨루일 클로라이드 (40 mmol)을 30 mL의 N,N-디메틸아세트아미드 용액에 녹인다. 0℃에서 세 시간 반응 시킨 후 5 mL의 피리딘을 가한다. 반응 용액을 0℃의 찬물에 부어 침전 시킨다. 침전물을 필터하여 얻은 다음, 진공 오븐에서 건조한다. 건조한 침전물을 메탄올에서 재결정하여 9.2 g의 흰색의 깨끗한 고체를 얻는다.6 g of 3-methylbenzoic acid hydrazide (40 mmol) and p-toluyl chloride (40 mmol) were dissolved in 30 mL of N, N-dimethylacetamide solution. After three hours of reaction at 0 ° C, 5 mL of pyridine is added. The reaction solution is poured into cold water at 0 캜 to precipitate. The precipitate is filtered off and then dried in a vacuum oven. The dry precipitate was recrystallized from methanol to give 9.2 g of a white, clear solid.
수득율: 82 %.Yield: 82%.
녹는점: 224-225℃.Melting point: 224-225 ℃.
1H-NMR (DMSO, ppm): ( 10.4 (s, 2H), 7.7 (m, 4H), 7.4 (m, 4H), 2.3 (s, 6H).1 H-NMR (DMSO, ppm): (10.4 (s, 2H), 7.7 (m, 4H), 7.4 (m, 4H), 2.3 (s, 6H).
원소분석 [분석치: C, 71.25; H, 5.97; N, 10.47. 이론치: C, 71.62; H, 6.01; N, 10.44.]Elemental analysis [Analytical value: C, 71.25; H, 5.97; N, 10.47. Theoretical values: C, 71.62; H, 6.01; N, 10.44.]
실시예 8 : 2,5-비스(4-메틸페닐)-1,3,4-옥시디아졸의 합성.Example 8: Synthesis of 2,5-bis (4-methylphenyl) -1,3,4-oxydiazole.
5 g의 비스(3-메틸페닐) 히드라진 (19 mmol)과 50 mL의 포스포릴 클로라이드를 80℃에서 16시간 반응시킨다. 반응 후 남아 있는 과량의 포스포릴 클로라이드를 제거한 다음, 물과 염화 메틸렌으로 추출한다. 염화 메틸렌 층을 분리하여 황산마그네슘으로 물을 제거한 다음, 용매를 로터리 증류기로 제거하고 남은 고체 화합물을 진공하에서 건조한다. 얻은 고체 화합물을 메탄올 용액에서 재결정하여 4.3 g의 깨끗한 고체 화합물을 얻는다.5 g of bis (3-methylphenyl) hydrazine (19 mmol) and 50 mL of phosphoryl chloride are reacted at 80 DEG C for 16 hours. The excess phosphoryl chloride remaining after the reaction is removed, followed by extraction with water and methylene chloride. The methylene chloride layer is separated, water is removed with magnesium sulfate, the solvent is removed with a rotary distiller, and the remaining solid compound is dried under vacuum. The obtained solid compound was recrystallized in methanol to obtain 4.3 g of a clean solid compound.
수득율: 91 %.Yield: 91%.
녹는점: 83-84℃.Melting point: 83-84 ℃.
1H-NMR (CDCl3, ppm): ( 7.9 (m, 4H), 7.4 (m, 4H), 2.4 (s, 6H).1 H-NMR (CDCl 3, ppm): 7.9 (m, 4H), 7.4 (m, 4H), 2.4 (s, 6H).
원소분석 [분석치: C, 76.25; H, 5.62; N, 11.36. 이론치: C, 76.78; H, 5.64; N, 11.19.]Elemental analysis [Analytical value: C, 76.25; H, 5.62; N, 11.36. Theoretical values: C, 76.78; H, 5.64; N, 11.19.]
실시예 9 : 2,5-비스[3-(브로모메틸)페닐]-1,3,4-옥시디아졸의 합성.Example 9: Synthesis of 2,5-bis [3- (bromomethyl) phenyl] -1,3,4-oxadiazole.
3.6 g의 2,5-비스(3-메틸페닐)-1,3,4-옥시디아졸 (14 mmol)과 5.5 g의 N-브로모숙신이미드 (28 mmol) 및 소량의 과산화 벤조산을 100 mL의 사염화탄소에 가한 후, 5시간 동안 환류하였다. 반응 후, 반응 용기 표면에 뜨는 숙신 이미드를 필터하여 제거하고 용매를 로터리 증류기로 제거한다. 생성된 고체 화합물을 메탄올에 씻어서 필터한 후, 진공 오븐에서 건조하여 4.3 g의 흰색 고체를 얻는다.A mixture of 3.6 g of 2,5-bis (3-methylphenyl) -1,3,4-oxadiazole (14 mmol), 5.5 g of N-bromosuccinimide (28 mmol) and a small amount of benzoyl peroxide Of carbon tetrachloride and refluxed for 5 hours. After the reaction, the succinimide floating on the surface of the reaction vessel is filtered out, and the solvent is removed with a rotary still. The resulting solid compound was rinsed in methanol and filtered, and then dried in a vacuum oven to obtain 4.3 g of a white solid.
수득율: 75 %.Yield: 75%.
녹는점: 162-164℃.Melting point: 162-164 ° C.
1H-NMR (CDCl3, ppm): ( 8.1 (m, 4H), 7.5 (m, 4H), 4.5 (s, 4H).1 H-NMR (CDCl 3, ppm): (8.1 (m, 4H), 7.5 (m, 4H), 4.5 (s, 4H).
원소분석 [분석치: C, 47.28; H, 2.99; N, 6.87. 이론치: C, 47.09; H, 2.96; N, 6.86.]Elemental analysis [Anal. C, 47.28; H, 2.99; N, 6.87. Theoretical values: C, 47.09; H, 2.96; N, 6.86.]
실시예 10: 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥시디아졸의 합성.Example 10: Synthesis of 2,5-bis (3-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole.
3.0 g (7mmol)의 2,5-비스[3-(브로모메틸)페닐]-1,3,4-옥시디아졸과 4.3 g (16 mmol)의 트리페닐 포스핀을 30 mL의 디메틸포름이미드 (DMF) 용액에 녹인 후, 24 시간 환류하였다. 반응 후, 용액을 과량의 디에틸 에테르에 부어 침전시켰다. 침전물을 디에틸 에테르로 여러 번 씻어준 다음, 필터하여 진공 오븐에서 건조하여 4.5 g의 흰색 고체를 얻는다.A mixture of 3.0 g (7 mmol) 2,5-bis [3- (bromomethyl) phenyl] -1,3,4-oxadiazole and 4.3 g (16 mmol) triphenylphosphine was dissolved in 30 mL of dimethylformamide (DMF) solution, and refluxed for 24 hours. After the reaction, the solution was poured into excess diethyl ether to precipitate. The precipitate is washed several times with diethyl ether, filtered and dried in a vacuum oven to give 4.5 g of a white solid.
수득율: 80 %.Yield: 80%.
녹는점: 197-198℃.Melting point: 197-198 ℃.
1H-NMR (CDCl3, ppm): ( 7.8-7.5 (m, 34H), 7.2 (m, 4H), 5.6 (d, 4H). 원소분석 [분석치: C, 66.62; H, 4.55; N, 3.11. 이론치: C, 66.97; H, 4.54; N,3.00.].1 H-NMR (CDCl 3, ppm): (7.8-7.5 (m, 34H), 7.2 (m, 4H), 5.6 (d, 4H). Elemental analysis [ Theoretical: C, 66.97; H, 4.54; N, 3.00.].
실시예 11 : 발광 고분자 P-3의 합성.Example 11: Synthesis of Emissive Polymer P-3.
1.47 g (16 mmol)의 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸(화학식 M-1)과 0.53 g (16 mmol)의 3,6-디포밀-9-(2-에틸헥실)-카바졸(화학식 M-3)를 15 mL의 클로로포름과 에탄올 혼합 용매에 녹인다. 2.7 g (40 mmol)의 염화 에톡사이드를 15 mL의 무수 에탄올에 녹인 다음, 상온에서 단량체 용액에 천천히 적가하여 24 시간 동안 반응시킨다. 반응 후, 반응 용액을 염화 메틸렌으로 추출한다. 로터리 증류기로 추출된 고분자 용액의 용매를 제거한 후 노란색의 고분자를 얻는다. 여러 번 수득한 고분자를 염화 메틸렌에 녹인 후 메탄올에 침전시켜 깨끗한 고분자 0.5 g을 얻는다.To a solution of 1.47 g (16 mmol) 2,5-bis (4-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole (M-1) and 0.53 g (16 mmol) , 6-dipalmyl-9- (2-ethylhexyl) -carbazole (M-3) is dissolved in a mixed solvent of 15 mL of chloroform and ethanol. 2.7 g (40 mmol) of chlorinated ethoxide was dissolved in 15 mL of anhydrous ethanol, slowly added dropwise to the monomer solution at room temperature, and allowed to react for 24 hours. After the reaction, the reaction solution is extracted with methylene chloride. After removing the solvent of the polymer solution extracted with the rotary distiller, a yellow polymer is obtained. The polymer obtained several times is dissolved in methylene chloride and precipitated in methanol to obtain 0.5 g of a clean polymer.
수득율: 50 %.Yield: 50%.
실시예 12 : 발광 고분자 P-4의 합성.Example 12: Synthesis of Emissive Polymer P-4.
1.47 g (16 mmol)의 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸(화학식 M-2)와 0.53 g (16 mmol)의 3,6-디포밀-9-(2-에틸헥실)-카바졸(화학식 M-3)를 15 mL의 클로로포름과 에탄올 혼합 용매에 녹인다. 2.7 g의 염화 에톡사이드를 15 mL의 무수 에탄올에 녹인 다음, 상온에서 단량체 용액에 천천히 적가하여 24 시간 동안 반응시킨다. 반응 후, 반응 용액을 염화 메틸렌으로 추출한다. 로터리 증류기로 추출된 고분자 용액의 용매를 제거한 후, 노란색의 고분자를 얻는다. 여러 번 수득한 고분자를 염화 메틸렌에 녹인 후, 메탄올에 침전시켜 깨끗한 고분자 0.40 g을 얻는다.To a solution of 1.47 g (16 mmol) 2,5-bis (3-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole (M-2) and 0.53 g (16 mmol) , 6-dipalmyl-9- (2-ethylhexyl) -carbazole (M-3) is dissolved in a mixed solvent of 15 mL of chloroform and ethanol. 2.7 g of chlorinated ethoxide is dissolved in 15 mL of anhydrous ethanol and slowly added dropwise to the monomer solution at room temperature for 24 hours. After the reaction, the reaction solution is extracted with methylene chloride. After removing the solvent of the polymer solution extracted with the rotary distiller, a yellow polymer is obtained. The polymer obtained several times is dissolved in methylene chloride and precipitated in methanol to obtain 0.40 g of a clear polymer.
수득율: 46 %.Yield: 46%.
실시예 13 : 발광 고분자 P-5의 합성.Example 13: Synthesis of Emissive Polymer P-5.
1.47 g (16 mmol)의 2,5-비스(4-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸(화학식 M-1)와 0.53 g (16 mmol)의(2-메톡시-5-(2'-에틸헥실옥시))테레프탈알데히드(화학식 M-4)를 15 mL의 클로로포름에 녹인다. 2.7 g (40 mmol)의 염화 에톡사이드를 15 mL의 무수 에탄올에 녹인 다음, 상온에서 단량체 용액에 천천히 적가하여 24 시간 동안 반응시킨다. 반응 후, 반응 용액을 염화 메틸렌으로 추출한다. 로터리 증류기로 추출된 고분자 용액의 용매를 제거한 후 노란색의 고분자를 얻는다. 여러 번 수득한 고분자를 염화 메틸렌에 녹인 후, 메탄올에 침전시켜 깨끗한 고분자 0.40 g을 얻는다.Of 1.47 g (16 mmol) 2,5- bis (4 weekends alkylene-triphenyl phosphonium bromide and Titanium) -1,3,4-oxadiazole (Formula M-1) and 0.53 g (16 mmol) ( (M-4) of 2-methoxy-5- (2'-ethylhexyloxy)) terephthalaldehyde is dissolved in 15 mL of chloroform. 2.7 g (40 mmol) of chlorinated ethoxide was dissolved in 15 mL of anhydrous ethanol, slowly added dropwise to the monomer solution at room temperature, and allowed to react for 24 hours. After the reaction, the reaction solution is extracted with methylene chloride. After removing the solvent of the polymer solution extracted with the rotary distiller, a yellow polymer is obtained. The polymer obtained several times is dissolved in methylene chloride and precipitated in methanol to obtain 0.40 g of a clear polymer.
수득율: 50 %.Yield: 50%.
실시예 14 : 발광 고분자 P-6의 합성.Example 14: Synthesis of Emissive Polymer P-6.
1.47 g의 2,5-비스(3-토일렌-트리페닐포스포니움 브로마이드)-1,3,4-옥사디아졸(화학식 M-2)와 0.53 g의(2-메톡시-5-(2'-에틸헥실옥시))테레프탈알데히드(화학식 M-4)를 15 mL의 클로로포름에 녹인다. 2.7 g의 염화 에톡사이드를 15 ml의 무수 에탄올에 녹인 다음, 상온에서 단량체 용액에 천천히 적가하여 24 시간 동안 반응시킨다. 반응 후, 반응 용액을 염화 메틸렌으로 추출한다. 로터리 증류기로 추출된 고분자 용액의 용매를 제거한 후, 노란색의 고분자를 얻는다. 여러 번 수득한 고분자를 염화 메틸렌에 녹인 후, 메탄올에 침전 시켜 깨끗한 고분자0.5 g을 얻는다.To a solution of 1.47 g 2,5-bis (3-toylene-triphenylphosphonium bromide) -1,3,4-oxadiazole (M-2) and 0.53 g (2-methoxy- 2'-ethylhexyloxy)) terephthalaldehyde (formula M-4) is dissolved in 15 mL of chloroform. 2.7 g of chlorinated ethoxide is dissolved in 15 ml of anhydrous ethanol and slowly added dropwise to the monomer solution at room temperature for 24 hours. After the reaction, the reaction solution is extracted with methylene chloride. After removing the solvent of the polymer solution extracted with the rotary distiller, a yellow polymer is obtained. The polymer obtained several times is dissolved in methylene chloride, and then precipitated in methanol to obtain 0.5 g of a clear polymer.
수득율: 70 %.Yield: 70%.
합성된 발광 고분자 P-3, P-4, P-5 그리고 P-6는 모두 일반 적인 유기 용매에 잘 용해되었으며, 발광 고분자 P-3은 약 390 nm 에서 최대 흡수를 보였고, P-4는 230 nm과 395 nm에서 최대 흡수를 보였으며, P-5는 340 nm와 395 nm 에서 최대 흡수 피크를 나타내었고, P-6는 300 nm와 405 nm에서 최대 흡수를 나타내었다. 도 2에 발광 고분자들의 흡수 스펙트럼을 도시하였다.All of the synthesized light emitting polymers P-3, P-4, P-5 and P-6 were well dissolved in a common organic solvent. The light emitting polymer P-3 exhibited maximum absorption at about 390 nm, P- nm and 395 nm, P-5 exhibited the maximum absorption peak at 340 nm and 395 nm, and P-6 exhibited maximum absorption at 300 nm and 405 nm. FIG. 2 shows absorption spectra of the light emitting polymers.
광 발광 (photoluminescence, PL) 스펙트럼은 발광 고분자 P-3이 청녹색인 495 nm, P-4가 청색 영역인 448 nm, 그리고 P-5가 녹색 영역인 508 nm에서 최대 발광 피크를 보였고, P-6가 475 nm의 청색 영역에서 발광 피크를 보였다. 도 3에 발광 고분자들의 발광 스펙트럼을 도시하였다.The peak emission peak at 498 nm, P-4 at 448 nm, and P-5 at 508 nm in the green region of the light emitting polymer P-3, P-6 Showed an emission peak in the blue region of 475 nm. FIG. 3 shows emission spectra of the light emitting polymers.
P-3을 발광층으로 하고 유리 위에 코팅된 ITO를 양극, 그리고 알루미늄을 음극으로 하는 단일층 전기 발광 소자를 제작하였다. 제작된 소자는 인가 전압의 증가에 따라 전류가 증가하는 전형적인 다이오드 특성을 보였고, 약 10 V 전후에서 눈으로 볼 수 있는 청녹색 발광을 하였다. ITO/P-1/Al 단일층 소자의 최대 밝기는 20 V 에서 500 cd/m2 으로서, 같은 조건에서 PPV 를 이용한 단일층 발광 소자 (ITO/PPV/Al)의 최대 밝기인 50 cd/m2 보다 월등히 높았다. 도 4에 단일층 발광 소자의 전류-전압 특성을, 그리고 도 5에 전압에 따른 발광 세기 특성을 도시하였다.A single layer electroluminescent device was fabricated using P-3 as a light emitting layer, ITO coated on glass as anode, and aluminum as cathode. The fabricated device showed a typical diode characteristic in which the current increases with an increase in the applied voltage. The maximum brightness of the ITO / P-1 / Al single layer device is 500 cd / m2 at 20 V, which is much higher than the maximum brightness of 50 cd / m2 of the single layer light emitting device (PPO / PPV / Respectively. FIG. 4 shows the current-voltage characteristics of the single-layer light-emitting device, and FIG. 5 shows the light-emission intensity characteristics according to the voltage.
상술한 바와 같이 본 발명에 따른 발광 고분자들은 한 고분자 사슬 내에 전자와 정공 수송 능력이 우수한 반복 단위가 함께 있도록 하여 전자와 정공의 주입을 용이하게 하고 여기자의 생성 확률을 높여 전기 발광 소자의 발광 효율을 크게 향상시킬 수 있는 효과가 있다.As described above, the light-emitting polymers according to the present invention have electron and hole repeating units together in a polymer chain, facilitating the injection of electrons and holes and increasing the probability of forming excitons, There is an effect that can be greatly improved.
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