KR100258593B1 - Silicon compounds for electroluminescent element - Google Patents
Silicon compounds for electroluminescent element Download PDFInfo
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- KR100258593B1 KR100258593B1 KR1019980011714A KR19980011714A KR100258593B1 KR 100258593 B1 KR100258593 B1 KR 100258593B1 KR 1019980011714 A KR1019980011714 A KR 1019980011714A KR 19980011714 A KR19980011714 A KR 19980011714A KR 100258593 B1 KR100258593 B1 KR 100258593B1
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- South Korea
- Prior art keywords
- copolymer
- cyanophenylenevinylene
- alkyl
- terephthalaldehyde
- prepared
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- 150000003377 silicon compounds Chemical class 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- -1 aryl silane Chemical compound 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract 3
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 52
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 8
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 8
- VMHCBSGWJYTOML-UHFFFAOYSA-N 9h-carbazole-1-carbaldehyde Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2C=O VMHCBSGWJYTOML-UHFFFAOYSA-N 0.000 claims description 5
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 6
- 239000001257 hydrogen Substances 0.000 claims 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 claims 2
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical class [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 99
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 38
- ISBXAFPBXLGRIP-UHFFFAOYSA-N hexyl(methyl)silicon Chemical compound CCCCCC[Si]C ISBXAFPBXLGRIP-UHFFFAOYSA-N 0.000 description 33
- KFDXCXLJBAVJMR-UHFFFAOYSA-N dibutylsilane Chemical compound CCCC[SiH2]CCCC KFDXCXLJBAVJMR-UHFFFAOYSA-N 0.000 description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 14
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000005401 electroluminescence Methods 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 229930192474 thiophene Natural products 0.000 description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- LMGNETAPCBMZFU-UHFFFAOYSA-N 2-[4-[[4-(cyanomethyl)phenyl]-diphenylsilyl]phenyl]acetonitrile Chemical compound C1=CC=C(C=C1)[Si](C2=CC=CC=C2)(C3=CC=C(C=C3)CC#N)C4=CC=C(C=C4)CC#N LMGNETAPCBMZFU-UHFFFAOYSA-N 0.000 description 2
- WBYSCMGRFQHFGW-UHFFFAOYSA-N CCCCCC[Si](C)(c1ccc(CC#N)cc1)c1ccc(CC#N)cc1 Chemical compound CCCCCC[Si](C)(c1ccc(CC#N)cc1)c1ccc(CC#N)cc1 WBYSCMGRFQHFGW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QROAAEYKZDADDB-UHFFFAOYSA-N BrCC1=CC=C(C=C1)[Si](C)(CCCCCC)C1=CC=C(C=C1)CBr Chemical compound BrCC1=CC=C(C=C1)[Si](C)(CCCCCC)C1=CC=C(C=C1)CBr QROAAEYKZDADDB-UHFFFAOYSA-N 0.000 description 1
- KXCBVWQSTVYLCN-UHFFFAOYSA-N CCCC[Si](CCCC)(c1ccc(CC#N)cc1)c1ccc(CC#N)cc1 Chemical compound CCCC[Si](CCCC)(c1ccc(CC#N)cc1)c1ccc(CC#N)cc1 KXCBVWQSTVYLCN-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- GPCLZPVSTFYHGM-UHFFFAOYSA-N bis[4-(bromomethyl)phenyl]-diphenylsilane Chemical compound C1=CC(CBr)=CC=C1[Si](C=1C=CC(CBr)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GPCLZPVSTFYHGM-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Silicon Polymers (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
본 발명은 실리콘을 함유하는 전기 발광 고분자 화합물에 관한 것으로서, 일반적인 유기 용매에 잘 녹고, 청색발광을 하면서 낮은 구동전압을 가지는 고분자재료 및 이의 제조 방법에 관한 발명이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroluminescent polymer compound containing silicon. The present invention relates to a polymer material having a low driving voltage while being well dissolved in a general organic solvent and emitting blue light, and a method of manufacturing the same.
차세대 정보 통신 시스템에 있어서는 다양한 영상 정보 서비스가 요구되고 있어 평판형 표시 소자 (display device)에 사용되는 소재로 전기 발광 고분자 재료를 사용하면 무기재료에 비하여 낮은 구동 전압, 청색-적색의 넓은 발광색을 낼 수 있고, 또한 고분자 소재의 뛰어난 가공성으로 인하여 평면상의 대형 디스플레이가 가능하기 때문에, 현재 많은 연구가 진행되고 있다.In the next-generation information and communication system, various image information services are required, and when the electroluminescent polymer material is used as the material used for the flat panel display device, it has lower driving voltage and wider blue-red color than the inorganic material. In addition, because of the excellent processability of the polymer material enables a large display on a flat surface, many studies are currently being conducted.
처음의 전기 발광 (electroluminescence : EL) 소자는 GaN, Zns, SiC 등의 무기물로 만들어졌다. 무기물로 만든 EL 소자는 가공이 어렵고 소비전력이 교류 200V 이상으로 높으며, 발광에도 한계가 있어 적ㆍ녹ㆍ청색의 전색 (full color)화가 힘들다. 그러나 1987년 Eastmann Kodak사에서 π-공액 구조를 가지는 aluminaquinone (Alq3)에서 EL이 발견된 이후, 유기물에서의 EL에 대한 연구가 활발해졌다 (C. W. Tang, and S. A. VanSlyke, Appl. Phys. Lett., 51, 913 (1987)). 유기물질은 분자구조가 단순하고 분자설계가 쉬우며, 합성이 용이하다. 그리고, 무기물질에서는 어려운 적ㆍ녹ㆍ청색의 전색화가 가능하다. 그러나 기계적 강도가 낮고, 열에 불안정한 단점이 있다. 이를 보완하고 유기물질의 장점을 살린 유기 고분자가 이용되기 시작했다. 유기 고분자는 1990년 캠브리지 대학에서 J. H. Burroughes 등이 poly(p-phenylenevinylene) (PPV)으로 만든 소자에서 EL이 발견된 이후로 유기 고분자에 대한 연구가 활발해지기 시작했다(J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burn, and A. B. Holmes, Nature, 347, 539 (1990)).The first electroluminescence (EL) devices were made of inorganic materials such as GaN, Zns, and SiC. EL elements made of inorganic materials are difficult to process, consume more than 200V of AC power, and are limited in light emission, making it difficult to achieve red, green, and blue full color. However, since EL was discovered in aluminaquinone (Alq 3 ) with π-conjugated structure at Eastmann Kodak in 1987, the study of EL in organic matter has been actively conducted (CW Tang, and SA VanSlyke, Appl. Phys. Lett., 51, 913 (1987)). Organic materials have simple molecular structure, easy molecular design, and easy synthesis. In addition, it is possible to harden red, green, and blue colors with inorganic materials. However, there are disadvantages of low mechanical strength and heat instability. Organic polymers that make up for this and take advantage of organic materials have begun to be used. Organic polymers have been active in the field of organic polymers since the discovery of EL in a device made of poly (p-phenylenevinylene) (PPV) by JH Burroughes et al. At the University of Cambridge in 1990 (JH Burroughes, DDC Bradley, AR Brown). , RN Marks, K. Mackay, RH Friend, PL Burn, and AB Holmes, Nature, 347, 539 (1990)).
일반적으로 PPV는 Wittig 반응 등에 의해서 합성이 가능하나, 이들 방법에 의해서 얻어진 중합체는 유기 용매에 잘 녹지 않으며, 분자량이 낮은 단점이 있다. 또한 박막형 LED 소자제작에 있어서 박막을 입히는데 어려움이 있다. 그래서 유기 용매에 잘 녹으며, 분자량도 큰 중합체를 얻는 방법으로, 수용성 전구체 (precursor)를 통해 PPV를 합성하는 방법이 널리 사용되고 있다. 수용성 전구체의 특징은 분자량의 순도를 높일 수 있고 변환되기 전에 원하는 형태로 제조할 수 있으며, 특히 다양한 두께를 갖고 밀도가 높은 필름을 스핀코팅 등의 방법으로 얻을 수 있다. 전구체를 이용한 PPV의 PL 최대 피크는 540nm로서 녹색의 빛을 발하며, 구동전압은 약 14V이다.In general, PPV can be synthesized by the Wittig reaction or the like, but the polymers obtained by these methods are poorly soluble in organic solvents, and have a low molecular weight. In addition, there is a difficulty in coating a thin film in manufacturing a thin film type LED device. Therefore, a method of synthesizing PPV through a water-soluble precursor (precursor) is widely used as a method for obtaining a polymer that is well dissolved in an organic solvent and has a high molecular weight. The characteristic of the water-soluble precursor can increase the purity of the molecular weight and can be prepared in the desired form before conversion, and in particular, a film having various thicknesses and high density can be obtained by spin coating or the like. The maximum peak PL of the PPV using the precursor is 540 nm, which emits green light, and the driving voltage is about 14V.
이외에도 용해도를 증가시키기 위하여 PPV의 페닐기에 알킬기나 알콕시기 등을 치환하기도 한다. 최근 높은 용해도로 많은 관심을 끌고 있는 물질로는 poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene)(MEH-PPV)이다(F. Wudl, S. Hoger, C. Zhang, K. Pakbaz, and A. J. Heeger, Polym. Preprint, 34, 197 (1993)). 이 MEH-PPV는 염화메틸렌, 테트로히드로퓨란, 사이클로헥사논 등의 일반적인 유기 용매에 잘 녹아 박막 형태로의 가공이 가능하다. MEH-PPV의 UV 최대 흡수 파장(λmax)은 510nm인데, 이는 페닐기에 치환된 전자 주게 dialkoxy기에 의해 PPV (λmax=420nm)보다 장파장쪽으로 이동한다. PL 스펙트럼도 PPV (540nm)에 비해 장파장으로 이동하며 약 590nm에서 최대 피크를 나타낸다. MEH-PPV의 구동전압은 약 4V이다.In addition, an alkyl group or an alkoxy group may be substituted for the phenyl group of PPV in order to increase the solubility. In recent years, the high solubility has attracted much attention as poly (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene) (MEH-PPV) (F. Wudl, S. Hoger, C. Zhang , K. Pakbaz, and AJ Heeger, Polym. Preprint, 34, 197 (1993)). This MEH-PPV is well dissolved in common organic solvents such as methylene chloride, tetrahydrofuran and cyclohexanone and can be processed into a thin film form. The UV maximum absorption wavelength (λ max ) of MEH-PPV is 510 nm, which is shifted toward longer wavelength than PPV (λ max = 420 nm) by the electron donor dialkoxy group substituted with a phenyl group. The PL spectrum also shifts to longer wavelengths compared to PPV (540 nm) and shows a maximum peak at about 590 nm. The drive voltage of MEH-PPV is about 4V.
PPV와 MEH-PPV의 발광 효율은 각각 0.1% 와 1%로 낮은 값을 가진다. 그래서 높은 발광 효율을 가지는 고분자를 얻기 위해서 많은 노력이 이루어졌다. 1993년 A. B. Holmes 팀에서 높은 발광 효율을 가지는 고분자를 발표하였다( N. C. Greenham, S. C. Moratil, D. D. C. Bradley, R. H. Friend, and A. B. Holmes, Nature, 365, 628 (1993)). 이는 전자 친화력이 큰 치환체(CN)를 도입 즉, 낮은 energy state를 갖는 고분자를 이용하여 발광 효율을 높였다. CN과 같은 전자 끌게 기를 치환함에 따라 energy state의 전하를 유도하고, 고분자-고분자 간의 계면에서 정공과 전자가 축적된다. 이러한 현상은 발광층 내에서 두 운반자(전자와 정공)의 만남을 용이하게 할 수 있고 효율의 상승이 일어난다. 이 때의 발광 효율은 4%로서 지금까지 보고된 발광 고분자중 가장 큰 값이다. 폴리(시아노테레프탈리덴)의 EL 최대 피크는 710nm로서 빨간색의 빛을 발한다.The luminous efficiencies of PPV and MEH-PPV have low values of 0.1% and 1%, respectively. Therefore, much effort has been made to obtain a polymer having a high luminous efficiency. In 1993, the A. B. Holmes team published polymers with high luminous efficiency (N. C. Greenham, S. C. Moratil, D. D. C. Bradley, R. H. Friend, and A. B. Holmes, Nature, 365, 628 (1993)). This increased luminous efficiency by introducing a substituent (CN) having a large electron affinity, that is, using a polymer having a low energy state. The substitution of electron drag groups such as CN induces charge in the energy state, and holes and electrons accumulate at the polymer-polymer interface. This phenomenon can facilitate the meeting of two carriers (electrons and holes) in the light emitting layer, and an increase in efficiency occurs. The luminous efficiency at this time is 4%, which is the largest value among the light emitting polymers reported so far. The EL maximum peak of poly (cyanoterephthalidene) is 710 nm, emitting red light.
위에서 설명한 PPV와 PPV 유도체 고분자는 청색의 빛을 내기가 어렵다. 그래서, PPV 사슬의 공액 길이를 균일하게 조절한 CNMBC (Conjugated-Nonconjugated Multiblock Copolymer) 고분자로부터 청색 발광이 가능한데, 이는 F. E. Karasz에 의해서 처음으로 보고되었다(Z. Yang, and F. E. Karasz, Macromolecules, 26, 1188 (1993)). CNMBC는 낮은 분자량의 유기 공액 분자가 청색발광 영역에서 EL 최대치를 낼 수 있고, 작은 분자들은 고분자 기질에 블렌드할 수 있다는 지식에 바탕을 두고 있다. 균일한 공액 길이를 갖는 단단한 블록은 발광색을 결정하는 전자적 전이의 밴드 갭을 조정하는 역할을 하고, 유연한 블록은 고분자의 용해도와 박막 질을 결정하는 데 기여한다. 이 CNMBC 고분자로 된 소자는 청색 발광을 하지만, 구동전압이 높은 것이 단점이다. 한 예로 CNMBC이며, PPV의 측사슬에 실리콘을 포함하는 PDSiPV (poly(1,3-propane- dioxy-1,4-phenylene-1,2-ethenylene( 2,5-bisThe PPV and PPV derivative polymers described above are difficult to emit blue light. Thus, blue light emission from a conjugated nonconjugated multiblock copolymer (CNMBC) polymer with uniformly controlled conjugated lengths of PPV chains is possible, first reported by FE Karasz (Z. Yang, and FE Karasz, Macromolecules, 26, 1188). (1993)). CNMBC is based on the knowledge that low molecular weight organic conjugated molecules can produce EL maximums in the blue emission region and small molecules can blend into the polymer matrix. Rigid blocks with uniform conjugate length serve to adjust the band gap of the electronic transition that determines the emission color, while flexible blocks contribute to the determination of the solubility and thin film quality of the polymer. The device made of CNMBC polymer emits blue light, but has a disadvantage of high driving voltage. One example is CNMBC, which contains silicon in the side chain of PPV (poly (1,3-propane-dioxy-1,4-phenylene-1,2-ethenylene (2,5-bis)
(trimethylsilyl)-1,4-phenylene)-1,2-ethenylene-1,4-phenylene)의 광발광 최대 피크는 470nm로 청록색의 빛을 나타내며, 구동전압은 약 23V로 기존의 다른 PPV보다 높다(T. Zyung, D. H. Hwang, I. N. Kang, H. K. Shim, W. Y. Hwang, and J. J. Kim, Chem, Mater.,7, 1499, (1995)).The maximum peak of photoluminescence of (trimethylsilyl) -1,4-phenylene) -1,2-ethenylene-1,4-phenylene) is 470 nm, which shows cyan light, and the driving voltage is about 23 V, which is higher than other conventional PPV ( T. Zyung, DH Hwang, IN Kang, HK Shim, WY Hwang, and JJ Kim, Chem, Mater., 7, 1499, (1995)).
발광 효율을 높이는 방법으로 앞에서 설명했던 고분자 물질에 전자 끌게 기를 치환하는 방법과 달리, 두가지 고분자 물질을 블렌드하여 높은 발광 효율을 얻으려고 많은 연구가 이루졌다(I. N. Kang, D. H. Hwang, H. K. Shim, T. Zyung, and J. J. Kim, Macromolecules, 29, 165 (1996)). 완전 π-공액된 고분자인 MEH-PPV와 CNMBC인 PDSiPV를 블렌드한 결과, MEH-PPV 단일 물질을 사용했을 때 보다, 약 500배의 높은 발광 효율의 나타내었다.Unlike the method of substituting an electron withdrawing group in the polymer material described above as a method of increasing the luminous efficiency, many studies have been made to blend the two polymer materials to obtain a high luminous efficiency (IN Kang, DH Hwang, HK Shim, T. Zyung, and JJ Kim, Macromolecules, 29, 165 (1996)). The blend of the fully π-conjugated polymer MEH-PPV and CNMBC PDSiPV showed about 500 times higher luminous efficiency than when MEH-PPV single material was used.
위와 같이, 기존의 발표된 전기발광 고분자들은 청색발광을 하면서 낮은 구동전압을 가지기가 어렵다.As described above, the existing published electroluminescent polymers are difficult to have low driving voltage while emitting blue light.
본 발명자들은 낮은 구동전압에서 청색발광을 얻고자, 주사슬에 실리콘을, 측사슬에 시아노 그룹을 도입한 전기 발광 고분자 물질을 개발하였다.The present inventors have developed an electroluminescent polymer material in which silicon is introduced into the main chain and cyano groups are introduced into the side chain to obtain blue light emission at a low driving voltage.
따라서, 본 발명의 목적은 용해도가 우수하고, 실리콘에 의한 공액길이의 제한으로 청색 발광을 할 뿐만 아니라, 시아노 그룹에 의해 낮은 구동 전압도 가지는 전기발광 고분자 화합물 및 이의 제조방법을 제공하는 것이다.Accordingly, it is an object of the present invention to provide an electroluminescent polymer compound having excellent solubility, not only blue light emission due to limitation of conjugated length by silicon, but also having a low driving voltage by cyano group, and a method for producing the same.
상기의 발명의 목적은 하기 화학식 (1)의 디-(p-시아노메틸페닐)알킬/아릴실란 및 이의 중합체에 의해 달성된다.The object of the above invention is achieved by di- (p-cyanomethylphenyl) alkyl / arylsilane of formula (1) and polymers thereof.
상기 식에서,Where
R 및 R'는 알킬 또는 아릴 그룹이다.R and R 'are alkyl or aryl groups.
유기 실리콘 단량체는 가공성을 향상시키고 π-공액 길이를 제한하여 청색발광 다이오드를 예측하는 방향족 또는 지방족 그룹을 포함한다. 바람직한 R 및 R' 기는 메틸, 헥실 또는 알킬기, 또는 페닐기이다.Organosilicon monomers contain aromatic or aliphatic groups that enhance processability and limit the π-conjugated length to predict blue light emitting diodes. Preferred R and R 'groups are methyl, hexyl or alkyl groups, or phenyl groups.
상기 일반식 (1)의 제조방법은 디-(p-브로모메틸페닐)알킬/아릴실란을 시안화나트륨과 반응시켜 얻는다.The production method of the general formula (1) is obtained by reacting di- (p-bromomethylphenyl) alkyl / arylsilane with sodium cyanide.
일반식 (1)의 단량체를 사용하여 중합을 하는 경우에는 예를 들어 본 발명의 단량체를 테레프탈알데히드, 플로렌알데히드, 티오펜알데히드, 카르바졸알데히드 또는 피리딘알데히드, 또는 그 유도체와 중합반응시켜 공중합체를 제조한다.When the polymerization is carried out using the monomer of the general formula (1), for example, the monomer of the present invention is polymerized with terephthalaldehyde, florenealdehyde, thiophenaldehyde, carbazolealdehyde or pyridinealdehyde, or a derivative thereof to copolymerize the copolymer. To prepare.
전체적인 화학반응식은 하기 반응식 1 및 2에 나타내었다. 반응식 1은 단량체의 합성과정을 반응식 2는 중합체의 합성과정을 나타낸 것이다.The overall chemical scheme is shown in Schemes 1 and 2 below. Scheme 1 shows the synthesis of monomers, and Scheme 2 shows the synthesis of polymers.
화학반응식 2에서는 일반식(I)의 단량체와 공중합되는 단량체로서 테레프탈알데히드를 사용한 것을 예로 나타내었으나, 이 외에도 플로렌알데히드, 티오펜알데히드, 카르바졸알데히드 또는 피리딘알데히드, 또는 그 유도체와 중합반응시켜 공중합체를 제조할 수 있다.In Chemical Scheme 2, terephthalaldehyde was used as a monomer copolymerized with the monomer of general formula (I), but in addition, it was polymerized with florenealdehyde, thiophenaldehyde, carbazolealdehyde or pyridinealdehyde, or derivatives thereof to form The coalescence can be prepared.
〔화학반응식 1〕[Chemical Reaction Formula 1]
상기 식에서, Where
R 및 R' 는 알킬 또는 아릴 그룹이다.R and R 'are alkyl or aryl groups.
(*위의 화합물 중에서 디-(p-브로모메틸페닐)디알킬/아릴실란 화합물과 디-(p-시아노메틸페닐)알킬실란의 재료는 특허출원(출원번호: 97-464) 중임.)(* Among the above compounds, the materials of the di- (p-bromomethylphenyl) dialkyl / arylsilane compound and the di- (p-cyanomethylphenyl) alkylsilane are patent applications (application number: 97-464).)
〔화학반응식 2〕[Chemical Reaction Formula 2]
상기 식에서,Where
R 및 R' 는 알킬 또는 아릴 그룹이다.R and R 'are alkyl or aryl groups.
다음의 실시예에 본 발명을 좀 더 상세하게 설명하였다.The present invention is explained in more detail in the following examples.
실시예Example
시약reagent
테레프탈알데히드, 카바졸알데히드, 티오펜디알데히드, 테트라부틸암모늄하이드록사이드는 알드리치사의 제품을 정제없이 사용하였고, 테트라하이드로퓨란, t-부틸알코올은 기존에 알려진 방법(D. D. Perrin, and Armarego, Purification of Laboratory Chemical, 3rd Ed., Pergamon Press (1988))에 의해 정제하여 사용하였다.Terephthalaldehyde, carbazolealdehyde, thiophendialdehyde, and tetrabutylammonium hydroxide were used without purification of Aldrich's products, and tetrahydrofuran and t-butyl alcohol were previously known methods (DD Perrin, and Armarego, Purification of Laboratory). Purified by Chemical, 3rd Ed., Pergamon Press (1988)).
일반적인 방법Common way
모든 신규의 화합물들은1H-NMR과 IR로 구조를 확인하였다.1H-NMR 스펙트럼은 Bruker AM-200, 300 분광기를 사용하여 기록하였고, 모든 화학적 이동도는 내부 표준물질 테트라메틸 실란에 대해 ppm 단위로 기록되었다. 별다른 언급이 없는 한, 클로로포름을 NMR용매로 사용하였다.All new compounds were identified by 1 H-NMR and IR. 1 H-NMR spectra were recorded using a Bruker AM-200, 300 spectrometer, and all chemical mobility was reported in ppm relative to the internal standard tetramethyl silane. Unless otherwise stated, chloroform was used as the NMR solvent.
IR 스펙트럼은 Perkin-Elmer Spectrometer를 사용하여 KBr 펠렛으로 측정하였다.IR spectra were measured on KBr pellets using a Perkin-Elmer Spectrometer.
UV-가시광선 흡수스펙트럼은 클로로포름 용매를 사용하여 Perkin-Elmer Spectrometer를 사용하여 측정하였다.UV-visible spectra were measured using a Perkin-Elmer Spectrometer using a chloroform solvent.
951TGA 및 910S DSC 모듈이 부착된 Dupont 990 열분석기를 사용하여 열중량 분석 및 시차주사열량을 각각 측정하였다.Thermogravimetric analysis and differential scanning calorimetry were measured using a Dupont 990 thermal analyzer equipped with 951 TGA and 910S DSC modules, respectively.
단량체 합성Monomer Synthesis
실시예 1 : 디-(p-시아노메틸페닐)헥실메틸실란Example 1 di- (p-cyanomethylphenyl) hexylmethylsilane
100㎖ 용량의 둥근바닥 플라스크에 2g의 디-(p-브로모메틸페닐)헥실메틸실란을 넣고 0.63g의 NaCN을 10㎖의 DMSO에 녹여 플라스크에 넣고 이 혼합물을 24시간동안 환류시켰다. 반응이 끝난후, 물을 붓고 디에틸에테르로 유기물을 추출하였다. 물로 세척한 다음 무수황산마그네슘으로 건조시킨 뒤 디에틸에테르를 제거하였다. 용리제로 헥산/에틸아세테이트(5/1)를 사용하여 칼럼크로마토그래피를 한 다음, 다시 테트라하이드로퓨란으로 다시 칼럼크로마토그래피로 갈색의 생성물을 얻었다. 생성물은 12g이었고 수율은 75%였다.In a 100 ml round bottom flask, 2 g of di- (p-bromomethylphenyl) hexylmethylsilane was added, 0.63 g of NaCN was dissolved in 10 ml of DMSO, and the mixture was refluxed for 24 hours. After the reaction was completed, water was poured and the organics were extracted with diethyl ether. After washing with water and drying over anhydrous magnesium sulfate, diethyl ether was removed. Column chromatography was performed using hexane / ethyl acetate (5/1) as the eluent, and then again by column chromatography using tetrahydrofuran to obtain a brown product. The product was 12 g and the yield was 75%.
IR (neat, ㎝-1): 1210, 964, 885 (Si-지방족); 1105, 750, (Si-Ph); 2250 (Ph-CH2CN)IR (neat, cm −1 ): 1210, 964, 885 (Si-aliphatic); 1105, 750, (Si-Ph); 2250 (Ph-CH 2 CN)
1H-NMR (CDCl3, ppm): 0.8-1.4 (m 16H, Si-지방족); 3.7 (s, 4H, 아릴 CH2); 7.4-7.5 (q, 8H, 아릴 CH) 1 H-NMR (CDCl 3 , ppm): 0.8-1.4 (m 16H, Si-aliphatic); 3.7 (s, 4H, aryl CH 2 ); 7.4-7.5 (q, 8H, aryl CH)
실시예 2 : 디-(p-시아노메틸페닐)디페닐실란Example 2 Di- (p-cyanomethylphenyl) diphenylsilane
100㎖ 용량의 둥근바닥 플라스크에 2g의 디-(p-브로모메틸페닐)디페닐실란을 넣고 0.46g의 NaCN을 10㎖의 DMSO에 녹여 플라스크에 넣고 이 혼합물을 24시간동안 환류시켰다. 반응이 끝난후, 물을 붓고 디에틸에테르로 유기물을 추출하였다. 물로 세척한 다음 무수황산마그네슘으로 건조시킨 뒤 디에틸에테르를 제거하였다. 수율은 75%였다.2 g of di- (p-bromomethylphenyl) diphenylsilane was added to a 100 ml round bottom flask, 0.46 g of NaCN was dissolved in 10 ml of DMSO, and the mixture was refluxed for 24 hours. After the reaction was completed, water was poured and the organics were extracted with diethyl ether. After washing with water and drying over anhydrous magnesium sulfate, diethyl ether was removed. Yield 75%.
IR (KBr 펠렛, ㎝-1): 1425, 1105, 750, (Si-Ph); 2250 (Ph-CH2CN)IR (KBr pellet, cm −1 ): 1425, 1105, 750, (Si-Ph); 2250 (Ph-CH 2 CN)
1H-NMR (CDCl3, ppm): 3.7 (s, 4H, 아릴 CH2); 7.2-7.6 (q, 18H, 아릴 CH) 1 H-NMR (CDCl 3 , ppm): 3.7 (s, 4H, aryl CH 2 ); 7.2-7.6 (q, 18H, aryl CH)
중합체 합성Polymer synthesis
실시예 3 : 헥실메틸실란/페닐렌/시아노페닐렌비닐렌 공중합체(HMCNPPV)Example 3 hexylmethylsilane / phenylene / cyanophenylenevinylene copolymer (HMCNPPV)
100㎖ 용량의 둥근바닥 플라스크에 동몰의 테레프탈알데히드 (0.42g, 0.003mol) 및 디-(p-시아노메틸페닐)헥실메틸실란 (1.13g, 0.003mol)을 넣고 테트라히드로푸란과 t-부틸알코올 4㎖에 용해시켰다(테트라히드로푸란 : t-부틸알코올=1:1). 50∼60℃로 유지시킨 다음, 0.16㏄의 테트라부틸암모니움하이드록사이드를 넣고 20분 반응시켰다. 메탄올에 침전시킨 뒤, 중합체를 여과하고 오븐에서 진공건조하였다. 수율은 25%로 갈색의 중합체 생성물을 얻었다. 중합체의 물성은 하기 표 1에 게재하였다. 중합체의 열적 성질 및 광학적 성질을 측정하여 표 2에 기재하였다.In a 100 ml round bottom flask, equimolar terephthalaldehyde (0.42 g, 0.003 mol) and di- (p-cyanomethylphenyl) hexylmethylsilane (1.13 g, 0.003 mol) were added, and tetrahydrofuran and t-butyl alcohol 4 Dissolved in mL (tetrahydrofuran: t-butyl alcohol = 1: 1). After maintaining at 50-60 degreeC, 0.16 Pa of tetrabutyl ammonium hydroxide was added, and it was made to react for 20 minutes. After precipitation in methanol, the polymer was filtered and vacuum dried in an oven. The yield was 25% to give a brown polymer product. Physical properties of the polymer are listed in Table 1 below. The thermal and optical properties of the polymers were measured and listed in Table 2.
실시예 4 : 디부틸실란/페닐렌/시아노페닐렌비닐렌 공중합체(BuCNPPV)Example 4 dibutylsilane / phenylene / cyanophenylenevinylene copolymer (BuCNPPV)
100㎖ 용량의 둥근바닥 플라스크에 동몰의 테레프탈알데히드 (0.29g, 0.002mol) 및 디-(p-시아노메틸페닐)디부틸실란 (0.8g, 0.002mol)을 넣고 테트라히드로푸란과 t-부틸알코올 4㎖에 용해시켰다(테트라히드로푸란 : t-부틸알코올=1:1). 50∼60℃로 유지시킨 다음, 0.12㏄의 테트라부틸암모니움하이드록사이드를 넣고 20분 반응시켰다. 메탄올에 침전시킨 뒤, 중합체를 여과하고 오븐에서 진공건조하였다. 수율은 23%로 갈색의 중합체 생성물을 얻었다. 중합체의 물성은 하기 표 1에 게재하였다. 중합체의 열적 성질 및 광학적 성질을 측정하여 표 2에 기재하였다.To a 100 ml round bottom flask, equimolar terephthalaldehyde (0.29 g, 0.002 mol) and di- (p-cyanomethylphenyl) dibutylsilane (0.8 g, 0.002 mol) were added, tetrahydrofuran and t-butyl alcohol 4 Dissolved in mL (tetrahydrofuran: t-butyl alcohol = 1: 1). After maintaining at 50-60 degreeC, tetrabutylammonium hydroxide of 0.12Pa was added, and it reacted for 20 minutes. After precipitation in methanol, the polymer was filtered and vacuum dried in an oven. The yield was 23% to give a brown polymer product. Physical properties of the polymer are listed in Table 1 below. The thermal and optical properties of the polymers were measured and listed in Table 2.
실시예 5 : 디페닐실란/페닐렌/시아노페닐렌비닐렌 공중합체(PhCNPPV)Example 5 diphenylsilane / phenylene / cyanophenylenevinylene copolymer (PhCNPPV)
100㎖ 용량의 둥근바닥 플라스크에 동몰의 테레프탈알데히드 (0.36g, 0.0027mol) 및 디-(p-시아노메틸페닐)디페닐실란 (1.0g, 0.0027mol)을 넣고 테트라히드로푸란과 t-부틸알코올 4㎖에 용해시켰다(테트라히드로푸란 : t-부틸알코올=1:1). 50∼60℃로 유지시킨 다음, 0.13㏄의 테트라부틸암모니움하이드록사이드를 넣고 20분 반응시켰다. 메탄올에 침전시킨 뒤, 중합체를 여과하고 오븐에서 진공건조하였다. 수율은 20%로 갈색의 중합체 생성물을 얻었다.In a 100 ml round bottom flask, equimolar terephthalaldehyde (0.36 g, 0.0027 mol) and di- (p-cyanomethylphenyl) diphenylsilane (1.0 g, 0.0027 mol) were added, followed by tetrahydrofuran and t-butyl alcohol. Dissolved in mL (tetrahydrofuran: t-butyl alcohol = 1: 1). After maintaining at 50-60 degreeC, tetrabutylammonium hydroxide of 0.13Pa was added, and it reacted for 20 minutes. After precipitation in methanol, the polymer was filtered and vacuum dried in an oven. Yield 20% to give a brown polymer product.
실시예 6 : 헥실메틸실란/카바졸/시아노페닐렌비닐렌 공중합체(HMCNPVK)Example 6 Hexylmethylsilane / carbazole / cyanophenylenevinylene copolymer (HMCNPVK)
테레프탈알데히드 대신에 카바졸알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / carbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that carbazole aldehyde was used instead of terephthalaldehyde.
실시예 7 : 디페닐실란/카바졸/시아노페닐렌비닐렌 공중합체(PhCNPVK)Example 7 diphenylsilane / carbazole / cyanophenylenevinylene copolymer (PhCNPVK)
테레프탈알데히드 대신에 카바졸알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / carbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that carbazolealdehyde was used instead of terephthalaldehyde.
실시예 8 : 헥실메틸실란/티오펜/시아노페닐렌비닐렌 공중합체(HMCNThV)Example 8 hexylmethylsilane / thiophene / cyanophenylenevinylene copolymer (HMCNThV)
테레프탈알데히드 대신에 티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / thiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that thiophenaldehyde was used instead of terephthalaldehyde.
실시예 9 : 디페닐실란/티오펜/시아노페닐렌비닐렌 공중합체(PhCNThV)Example 9 diphenylsilane / thiophene / cyanophenylenevinylene copolymer (PhCNThV)
테레프탈알데히드 대신에 티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / thiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that thiophenaldehyde was used instead of terephthalaldehyde.
실시예 10 : 헥실메틸실란/피리딘/시아노페닐렌비닐렌 공중합체(HMCNPyV)Example 10 hexylmethylsilane / pyridine / cyanophenylenevinylene copolymer (HMCNPyV)
테레프탈알데히드 대신에 피리딘알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/피리딘/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / pyridine / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that pyridinealdehyde was used instead of terephthalaldehyde.
실시예 11 : 디페닐실란/피리딘/시아노페닐렌비닐렌 공중합체(PhCNPyV)Example 11 Diphenylsilane / Pyridine / Cyanophenylenevinylene Copolymer (PhCNPyV)
테레프탈알데히드 대신에 피리딘알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/피리딘/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / pyridine / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that pyridinealdehyde was used instead of terephthalaldehyde.
실시예 12 :Example 12:
헥실메틸실란/알콕시페닐렌/시아노페닐렌비닐렌 공중합체(HMCNAKPPV)Hexylmethylsilane / alkoxyphenylene / cyanophenylenevinylene copolymer (HMCNAKPPV)
테레프탈알데히드 대신에 알콕시페닐렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/알콕시페닐렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxyphenylene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxyphenylenealdehyde was used instead of terephthalaldehyde.
실시예 13 : 디페닐실란/알콕시페닐렌/시아노페닐렌비닐렌 공중합체(PhCNAKPPV)Example 13: diphenylsilane / alkoxyphenylene / cyanophenylenevinylene copolymer (PhCNAKPPV)
테레프탈알데히드 대신에 알콕시페닐렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/알콕시페닐렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxyphenylene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxyphenylenealdehyde was used instead of terephthalaldehyde.
실시예 14 : 헥실메틸실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체(HMCNAKThV)Example 14 Hexylmethylsilane / alkoxythiophene / cyanophenylenevinylene copolymer (HMCNAKThV)
테레프탈알데히드 대신에 알콕시티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxythiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxythiophenaldehyde was used instead of terephthalaldehyde.
실시예 15 : 디페닐실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체(PhCNAKThV)Example 15 Diphenylsilane / Alkoxythiophene / Cyanophenylenevinylene Copolymer (PhCNAKThV)
테레프탈알데히드 대신에 알콕시티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxythiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxythiophenaldehyde was used instead of terephthalaldehyde.
실시예 16 : 헥실메틸실란/플로렌/시아노페닐렌비닐렌 공중합체(HMCNPAF)Example 16 Hexylmethylsilane / Florene / Cyanophenylenevinylene Copolymer (HMCNPAF)
테레프탈알데히드 대신에 플로렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / florene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that florenealdehyde was used instead of terephthalaldehyde.
실시예 17 : 디페닐실란/플로렌/시아노페닐렌비닐렌 공중합체(PhCNPAF)Example 17 Diphenylsilane / Florene / Cyanophenylenevinylene Copolymer (PhCNPAF)
테레프탈알데히드 대신에 플로렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 디페닐실란/플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / florene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that florenealdehyde was used instead of terephthalaldehyde.
실시예 18 : 헥실메틸실란/알콕시카바졸/시아노페닐렌비닐렌 공중합체(SiHMCNAkPVK)Example 18 Hexylmethylsilane / alkoxycarbazole / cyanophenylenevinylene copolymer (SiHMCNAkPVK)
테레프탈알데히드 대신에 알콕시카바졸알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/알콕시카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / alkoxycarbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxycarbazole aldehyde was used instead of terephthalaldehyde.
실시예 19 : 디부틸실란/알콕시카바졸/시아노페닐렌비닐렌 공중합체(SiBuCNAkPVK)Example 19 dibutylsilane / alkoxycarbazole / cyanophenylenevinylene copolymer (SiBuCNAkPVK)
테레프탈알데히드 대신에 알콕시카바졸알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/알콕시카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / alkoxycarbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except that alkoxycarbazole aldehyde was used instead of terephthalaldehyde.
실시예 20 : 디페닐실란/알콕시카바졸/시아노페닐렌비닐렌 공중합체(SiPhCNAkPVK)Example 20 diphenylsilane / alkoxycarbazole / cyanophenylenevinylene copolymer (SiPhCNAkPVK)
테레프탈알데히드 대신에 알콕시카바졸알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/알콕시카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxycarbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that alkoxycarbazole aldehyde was used instead of terephthalaldehyde.
실시예 21 : 헥실메틸실란/아릴카바졸/시아노페닐렌비닐렌 공중합체(SiHMCNArPVK)Example 21 hexylmethylsilane / arylcarbazole / cyanophenylenevinylene copolymer (SiHMCNArPVK)
테레프탈알데히드 대신에 아릴카바졸알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/아릴카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / arylcarbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that arylcarbazole aldehyde was used instead of terephthalaldehyde.
실시예 22 : 디부틸실란/아릴카바졸/시아노페닐렌비닐렌 공중합체(SiBuCNArPVK)Example 22 Dibutylsilane / Arylcarbazole / Cyanophenylenevinylene Copolymer (SiBuCNArPVK)
테레프탈알데히드 대신에 아릴카바졸알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/아릴카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / arylcarbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except for using arylcarbazole aldehyde instead of terephthalaldehyde.
실시예 23 : 디페닐실란/아릴카바졸/시아노페닐렌비닐렌 공중합체(SiPhCNArPVK)Example 23 diphenylsilane / arylcarbazole / cyanophenylenevinylene copolymer (SiPhCNArPVK)
테레프탈알데히드 대신에 아릴카바졸알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/아릴카바졸/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / arylcarbazole / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that arylcarbazole aldehyde was used instead of terephthalaldehyde.
실시예 24 : 헥실메틸실란/티오펜/시아노페닐렌비닐렌 공중합체(SiHMCNThV)Example 24 hexylmethylsilane / thiophene / cyanophenylenevinylene copolymer (SiHMCNThV)
테레프탈알데히드 대신에 티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / thiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that thiophenaldehyde was used instead of terephthalaldehyde.
실시예 25 : 디부틸메틸실란/티오펜/시아노페닐렌비닐렌 공중합체(SiBuCNThV)Example 25 dibutylmethylsilane / thiophene / cyanophenylenevinylene copolymer (SiBuCNThV)
테레프탈알데히드 대신에 티오펜알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / thiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except that thiophenaldehyde was used instead of terephthalaldehyde.
실시예 26 : 디페닐실란/티오펜/시아노페닐렌비닐렌 공중합체(SiPhCNThV)Example 26 diphenylsilane / thiophene / cyanophenylenevinylene copolymer (SiPhCNThV)
테레프탈알데히드 대신에 티오펜알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / thiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that thiophenaldehyde was used instead of terephthalaldehyde.
실시예 27 : 헥실메틸실란/알킬티오펜/시아노페닐렌비닐렌 공중합체(SiHMCNAThV)Example 27 Hexylmethylsilane / alkylthiophene / cyanophenylenevinylene copolymer (SiHMCNAThV)
테레프탈알데히드 대신에 알킬티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/알킬티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / alkylthiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkylthiophenaldehyde was used instead of terephthalaldehyde.
실시예 28 : 디부틸실란/알킬티오펜/시아노페닐렌비닐렌 공중합체(SiBuCNAThV)Example 28 dibutylsilane / alkylthiophene / cyanophenylenevinylene copolymer (SiBuCNAThV)
테레프탈알데히드 대신에 알킬티오펜알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/알킬티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / alkylthiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except that alkylthiophenaldehyde was used instead of terephthalaldehyde.
실시예 29 : 디페닐실란/알킬티오펜/시아노페닐렌비닐렌 공중합체(SiPhCNAThV)Example 29 Diphenylsilane / Alkylthiophene / Cyanophenylenevinylene Copolymer (SiPhCNAThV)
테레프탈알데히드 대신에 알킬티오펜알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/알킬티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkylthiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except for using alkylthiophenaldehyde instead of terephthalaldehyde.
실시예 30 : 헥실메틸실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체(SiHMCNAkThV)Example 30 hexylmethylsilane / alkoxythiophene / cyanophenylenevinylene copolymer (SiHMCNAkThV)
테레프탈알데히드 대신에 알콕시티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / alkoxythiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxythiophenaldehyde was used instead of terephthalaldehyde.
실시예 31 : 디부틸실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체(SiBuCNAkThV)Example 31 dibutylsilane / alkoxythiophene / cyanophenylenevinylene copolymer (SiBuCNAkThV)
테레프탈알데히드 대신에 알콕시티오펜알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / alkoxythiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except that alkoxythiophenaldehyde was used instead of terephthalaldehyde.
실시예 32 : 디페닐실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체(SiPhCNAkThV)Example 32 diphenylsilane / alkoxythiophene / cyanophenylenevinylene copolymer (SiPhCNAkThV)
테레프탈알데히드 대신에 알콕시티오펜알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/알콕시티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxythiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that alkoxythiophenaldehyde was used instead of terephthalaldehyde.
실시예 33 : 헥실메틸실란/아릴티오펜/시아노페닐렌비닐렌 공중합체(SiHMCNArThV)Example 33 hexylmethylsilane / arylthiophene / cyanophenylenevinylene copolymer (SiHMCNArThV)
테레프탈알데히드 대신에 아릴티오펜알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/아릴티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / arylthiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that arylthiophenaldehyde was used instead of terephthalaldehyde.
실시예 34 : 디부틸실란/아릴티오펜/시아노페닐렌비닐렌 공중합체(SiBuCNAkThV)Example 34 dibutylsilane / arylthiophene / cyanophenylenevinylene copolymer (SiBuCNAkThV)
테레프탈알데히드 대신에 아릴티오펜알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/아릴티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / arylthiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except for using arylthiophenaldehyde instead of terephthalaldehyde.
실시예 35 : 디페닐실란/아릴티오펜/시아노페닐렌비닐렌 공중합체(SiPhCNAkThV)Example 35 diphenylsilane / arylthiophene / cyanophenylenevinylene copolymer (SiPhCNAkThV)
테레프탈알데히드 대신에 아릴티오펜알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/아릴티오펜/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / arylthiophene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except for using arylthiophenaldehyde instead of terephthalaldehyde.
실시예 36 : 헥실메틸실란/피리딘/시아노페닐렌비닐렌 공중합체(SiHMCNPyV)Example 36 hexylmethylsilane / pyridine / cyanophenylenevinylene copolymer (SiHMCNPyV)
테레프탈알데히드 대신에 피리딘알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/피리딘/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / pyridine / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that pyridinealdehyde was used instead of terephthalaldehyde.
실시예 37 : 디부틸실란/피리딘/시아노페닐렌비닐렌 공중합체(SiBuCNPyV)Example 37 dibutylsilane / pyridine / cyanophenylenevinylene copolymer (SiBuCNPyV)
테레프탈알데히드 대신에 피리딘알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/피리딘/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / pyridine / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except that pyridinealdehyde was used instead of terephthalaldehyde.
실시예 38 : 디페닐실란/피리딘/시아노페닐렌비닐렌 공중합체(SiPhCNPyV)Example 38 Diphenylsilane / Pyridine / Cyanophenylenevinylene Copolymer (SiPhCNPyV)
테레프탈알데히드 대신에 피리딘알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/피리딘/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / pyridine / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that pyridinealdehyde was used instead of terephthalaldehyde.
실시예 39 : 헥실메틸실란/플로렌/시아노페닐렌비닐렌 공중합체(SiHMCNPAF)Example 39 hexylmethylsilane / florene / cyanophenylenevinylene copolymer (SiHMCNPAF)
테레프탈알데히드 대신에 플로렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / florene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that florenealdehyde was used instead of terephthalaldehyde.
실시예 40 : 디부틸실란/플로렌/시아노페닐렌비닐렌 공중합체(SiBuCNPAF)Example 40 Dibutylsilane / Florene / Cyanophenylenevinylene Copolymer (SiBuCNPAF)
테레프탈알데히드 대신에 플로렌알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / florene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except that florenealdehyde was used instead of terephthalaldehyde.
실시예 41 : 디페닐실란/플로렌/시아노페닐렌비닐렌 공중합체(SiPhCNPAF)Example 41 Diphenylsilane / Florene / Cyanophenylenevinylene Copolymer (SiPhCNPAF)
테레프탈알데히드 대신에 플로렌알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / florene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that florenealdehyde was used instead of terephthalaldehyde.
실시예 42 : 헥실메틸실란/알킬플로렌/시아노페닐렌비닐렌 공중합체(SiHMCNAPAF)Example 42 Hexylmethylsilane / Alkylfluorene / Cyanophenylenevinylene Copolymer (SiHMCNAPAF)
테레프탈알데히드 대신에 알킬플로렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/알킬플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / alkylfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except for using alkylfluorene aldehyde instead of terephthalaldehyde.
실시예 43 : 디부틸실란/알킬플로렌/시아노페닐렌비닐렌 공중합체(SiBuCNAPAF)Example 43 Dibutylsilane / Alkylfluorene / Cyanophenylenevinylene Copolymer (SiBuCNAPAF)
테레프탈알데히드 대신에 알킬플로렌알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/알킬플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / alkylfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except for using alkylfluorene aldehyde instead of terephthalaldehyde.
실시예 44 : 디페닐실란/알킬플로렌/시아노페닐렌비닐렌 공중합체(SiPhCNAPAF)Example 44 Diphenylsilane / Alkylfluorene / Cyanophenylenevinylene Copolymer (SiPhCNAPAF)
테레프탈알데히드 대신에 알킬플로렌알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/알킬플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkylfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that alkylfluorene aldehyde was used instead of terephthalaldehyde.
실시예 45 : 헥실메틸실란/알콕시플로렌/시아노페닐렌비닐렌 공중합체(SiHMCNAkPAF)Example 45 Hexylmethylsilane / alkoxyfluorene / cyanophenylenevinylene copolymer (SiHMCNAkPAF)
테레프탈알데히드 대신에 알콕시플로렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/알콕시플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / alkoxyfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that alkoxyfluorene aldehyde was used instead of terephthalaldehyde.
실시예 46 : 디부틸실란/알콕시플로렌/시아노페닐렌비닐렌 공중합체(SiBuCNAkPAF)Example 46 dibutylsilane / alkoxyfluorene / cyanophenylenevinylene copolymer (SiBuCNAkPAF)
테레프탈알데히드 대신에 알콕시플로렌알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/알콕시플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / alkoxyfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except for using alkoxyfluorene aldehyde instead of terephthalaldehyde.
실시예 47 : 디페닐실란/알콕시플로렌/시아노페닐렌비닐렌 공중합체(SiPhCNAkPAF)Example 47 diphenylsilane / alkoxyfluorene / cyanophenylenevinylene copolymer (SiPhCNAkPAF)
테레프탈알데히드 대신에 알콕시플로렌알데히드를 사용하는 것을 제외하고는 실시예 5와 동일한 방법으로 디페닐실란/알콕시플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / alkoxyfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that alkoxyfluorene aldehyde was used instead of terephthalaldehyde.
실시예 48 : 헥실메틸실란/아릴플로렌/시아노페닐렌비닐렌 공중합체(SiHMCNArPAF)Example 48 hexylmethylsilane / arylfluorene / cyanophenylenevinylene copolymer (SiHMCNArPAF)
테레프탈알데히드 대신에 아릴플로렌알데히드를 사용하는 것을 제외하고는 실시예 3과 동일한 방법으로 헥실메틸실란/아릴플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A hexylmethylsilane / arylflorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 3 except that arylflorenealdehyde was used instead of terephthalaldehyde.
실시예 49 : 디부틸실란/아릴플로렌/시아노페닐렌비닐렌 공중합체(SiBuCNArPAF)Example 49 dibutylsilane / arylfluorene / cyanophenylenevinylene copolymer (SiBuCNArPAF)
테레프탈알데히드 대신에 아릴플로렌알데히드를 사용하는 것을 제외하고는 실시예 4와 동일한 방법으로 디부틸실란/아릴플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A dibutylsilane / aryl fluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 4 except for using aryl florene aldehyde instead of terephthalaldehyde.
실시예 50 : 디페닐실란/아릴플로렌/시아노페닐렌비닐렌 공중합체(SiPhCNArPAF)Example 50 Diphenylsilane / Arylfluorene / Cyanophenylenevinylene Copolymer (SiPhCNArPAF)
테레프탈알데히드 대신에 아릴플로렌알데히드를 사용하는 것을 제외하고는 실시예 5와동일한 방법으로 디페닐실란/아릴플로렌/시아노페닐렌비닐렌 공중합체를 제조하였다.A diphenylsilane / arylfluorene / cyanophenylenevinylene copolymer was prepared in the same manner as in Example 5 except that arylflorenealdehyde was used instead of terephthalaldehyde.
* 중합체의 수평균분자량, 중량평균분자량 및 분자량분포도계수는 폴리스티렌을 표준물질로 사용하는 겔 투과 크로마토그래피로 측정하였다.* The number average molecular weight, weight average molecular weight and molecular weight distribution coefficient of the polymer were measured by gel permeation chromatography using polystyrene as a standard.
표 1은 헥실메틸실란/페닐렌/시아노페닐렌비닐렌 공중합체(HMCNPPV)와 디부틸실란/페닐렌/시아노페닐렌비닐렌 공중합체(BuCNPPV)의 물성을 나타나낸 것이다. 수율은 23∼25%, 수평균분자량과 중량평균분자량은 각각 3900∼4200, 5400∼6000범위 였으며, 분자량 분포도 계수는 1.38∼1.42였다.Table 1 shows the physical properties of hexylmethylsilane / phenylene / cyanophenylenevinylene copolymer (HMCNPPV) and dibutylsilane / phenylene / cyanophenylenevinylene copolymer (BuCNPPV). The yield was 23-25%, the number average molecular weight and the weight average molecular weight were in the range of 3900-4200 and 5400-6000, respectively, and the molecular weight distribution coefficients were 1.38-1.42.
* 질량의 최초 손실이 나타날 때의 온도.* The temperature at which the initial loss of mass appears.
표 2는 디부틸실란/페닐렌/시아노페닐렌비닐렌 공중합체(BuCNPPV)의 열적 성질 및 광학적 성질을 나타낸 것이다. DSC에 의해 측정된 공중합체의 유리전이온도는 82℃였으며, TGA에 의한 열 안정성을 조사한 결과 질소대기하에서 206℃ 정도에서 초기분해를 보였다. 공중합체의 UV-Visible 흡수 스펙트럼은 345nm에서 최대흡수 파장을 보였으며, PL 발광 스펙트럼은 466 nm 사이에서 최대발광을 보였다. 그리고, EL 발광 스펙트럼은 약 480 nm에서 최대발광을 보였으며, I-V 특성에서는 약 7V에서 전류가 흐르기 시작하는 것을 알 수 있었다.Table 2 shows the thermal and optical properties of the dibutylsilane / phenylene / cyanophenylenevinylene copolymer (BuCNPPV). The glass transition temperature of the copolymer measured by DSC was 82 ° C, and thermal stability by TGA showed initial decomposition at about 206 ° C under nitrogen atmosphere. The UV-Visible absorption spectrum of the copolymer showed a maximum absorption wavelength at 345 nm, and the PL emission spectrum showed a maximum emission between 466 nm. In addition, the EL emission spectrum showed the maximum emission at about 480 nm, and the I-V characteristics showed that current began to flow at about 7V.
본 발명의 결과로부터 실리콘이 공액이중결합 골격 주사슬에 도입되면 공액이중결합이 전자이동을 편재화하여 청색발광을 얻을 수 있고, 시아노그룹이 측사슬에 치환되어 구동전압이 낮은 것을 알 수 있다.From the results of the present invention, it can be seen that when the silicon is introduced into the conjugated double bond backbone main chain, the conjugated double bond localizes electron transfer to obtain blue light emission, and the cyano group is substituted on the side chain to lower driving voltage. .
본 발명의 중합체는 실리콘을 함유하는 단량체를 먼저 합성한 후, knoevenagel 반응에 의해 합성되었다. 주사슬에 실리콘이 결합된 중합체는 보통의 유기 용매에 대해 좋은 용해도를 나타내고, 우수한 물리적 특성을 나타낸다.The polymer of the present invention was synthesized by knoevenagel reaction after first synthesizing the monomer containing silicon. Polymers in which the silicon is bonded to the main chain show good solubility in ordinary organic solvents and excellent physical properties.
본 발명의 중합체는 전기발광이 480nm로 청색발광을 하며, 구동전압은 약 7V로 기존의 중합체보다 구동전압이 낮음을 알 수 있다.The polymer of the present invention exhibits blue light emission at 480 nm, and the driving voltage is about 7 V, indicating that the driving voltage is lower than that of the conventional polymer.
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