KR20050047210A - Synthesis of new el polymer including conductive polymer and inorganic metals - Google Patents

Synthesis of new el polymer including conductive polymer and inorganic metals Download PDF

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KR20050047210A
KR20050047210A KR1020030081002A KR20030081002A KR20050047210A KR 20050047210 A KR20050047210 A KR 20050047210A KR 1020030081002 A KR1020030081002 A KR 1020030081002A KR 20030081002 A KR20030081002 A KR 20030081002A KR 20050047210 A KR20050047210 A KR 20050047210A
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polymer
synthesis
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light emitting
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황덕해
오동원
박미숙
송지영
사공은
이우붕
최영철
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최영철
오동원
이우붕
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence

Abstract

본 발명은 유무기전계발광 소자의 발광층으로 사용될 수 있는 하기 화학식으로 나타낸 단량체와 이를 포함하는 플로렌계 고분자 발광물질에 관한 것으로 하기 화학식으로 표시되는 구조의 유무기 발광체를 포함한다. 또한 본 발명은 높은 일함수를 갖는 양극과 낮은 일함수를 갖는 음극의 사이에 위치하는 적어도 하나의 유기물층을 포함하는 유기 전계발광 소자를 제공한다.The present invention relates to a monomer represented by the following formula that can be used as the light emitting layer of the organic electroluminescent device and a florene-based polymer light emitting material including the same, and includes an organic-inorganic emitter having a structure represented by the following formula. The present invention also provides an organic electroluminescent device comprising at least one organic material layer positioned between an anode having a high work function and a cathode having a low work function.

Description

전도성고분자와 무기금속을 포함하는 새로운 발광고분자의 제조법 {Synthesis of new EL polymer including conductive polymer and inorganic metals} Synthesis of new EL polymer including conductive polymer and inorganic metals

본 발명은 전계 발광소자의 발광재료용 플로렌계 중합체 및 이를 이용한 전계 발광소자에 관한 것으로 화학식1의 구조를 가진다. 유기 전계발광 소자는 투명 전극(양극)과 금속 전극(음극)사이에 발광층을 만들고 제조된 소자에 전압을 가하면 일반적으로 양극에서는 전공이 음극에서는 전자가 투입되고 이들이 반대전극으로 이동하면서 재결합하여 엑시톤이 되고 싱글렛디케이가 일어나면 발광하는 LED가 된다. 현재 저분자 유기EL의 경우는 기계적 강도가 낮고 열에 약하다는 단점이 있지만 고분자 재료 연구가 활발해지면서 이런 문제는 상당히 극복된 상태이다. 가장 대표적으로 알려진 고분자계 발광재료는 폴리페닐렌비닐렌(Poly(phenylenevinylene) 이하 PPV라 칭함) 폴리페닐렌(Poly(p-phenylene) 이하 PPP라 칭함) 고분자이며, 지금까지는 주로 이러한 고분자 재료들에 대한 연구가 이루어져 왔으나 유기용매에 녹지 않는다든지, 양자효율이 작은 단점이 있다. 또한 적당한 치환기를 분자의 주쇄나 측쇄에 도입함으로써 가공성이 향상되고 청색, 녹색, 및 적색의 다양한 빛을 나타내는 PPV나 PTh 유도체들도 있지만 여전히 제조공정이 복잡하고 안정성에 문제점을 갖고 있다.The present invention relates to a florene polymer for a light emitting material of an electroluminescent device and an electroluminescent device using the same, having a structure of Chemical Formula 1. In the organic electroluminescent device, a light emitting layer is formed between the transparent electrode (anode) and the metal electrode (cathode), and when a voltage is applied to the manufactured device, electrons are generally injected at the anode and electrons are injected at the cathode, and they move to the opposite electrode to recombine and excitons When a single red light occurs, it becomes an LED which emits light. In the case of low molecular organic EL, the mechanical strength is low and the heat is weak. However, as the research of polymer materials is active, this problem has been overcome. The most known polymeric light emitting materials are polyphenylenevinylene (hereinafter referred to as PPV) polyphenylene (Poly (p-phenylene) or below PPP) polymer, and so far, mainly Although research has been conducted, it does not dissolve in organic solvents or has a disadvantage of small quantum efficiency. In addition, there are some PPV or PTh derivatives which improve the processability by introducing suitable substituents into the main chain or the side chain of the molecule and exhibit various light of blue, green, and red, but still have a complicated manufacturing process and problems in stability.

이에 본 발명에서는 제조방법이 간단하면서도 유기 용매에 잘 녹아 공정이 간단한 장점을 가지는 고분자 EL 재료를 제조하기 위하여 부단히 연구한 결과 본 발명에 도달하게 되었다.Accordingly, in the present invention, the present invention has been steadily studied in order to prepare a polymer EL material having a simple process but simple dissolving in an organic solvent.

본 발명은 고분자계 EL소자를 제조할 때 화학식1을 함유하는 중합체를 발광재료로 말단기인 플로렌에 무기금속을 결합하여 사용하는 것을 특징으로 하고 있다. The present invention is characterized in that a polymer containing the formula (1) is used as a light emitting material by combining an inorganic metal with florene as an end group when manufacturing a polymer EL device.

화학식1 Formula 1

R은 알킬기(부틸기, 헥실기, 옥틸기등 탄소수가1~22개)이고, M은 무기금속(Eu, Pd, Sn, Ir, Zn, Cu, Ag, Pt, Ni, Au등)이고, X는 Ph, 알킬기 또는 H이다. R is an alkyl group (1-22 carbon atoms such as butyl group, hexyl group, octyl group), M is an inorganic metal (Eu, Pd, Sn, Ir, Zn, Cu, Ag, Pt, Ni, Au, etc.), X is Ph, an alkyl group or H.

본 발명은 플로렌계 유도체로서 열적안정성이 우수하고 X가 Eu일때 발광파장이 420nm, 530nm(λmax)이다.The present invention has excellent thermal stability as the florene derivative and the emission wavelength is 420 nm and 530 nm (λ max ) when X is Eu.

이하, 본 발명을 보다 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

먼저 새로운 단량체인 2,7-디브로모-9,9'-디벤질리데닐플로렌 합성이다. 반응식은 아래와 같다.First is a new monomer, 2,7-dibromo-9,9'-dibenzylideneylfluorene synthesis. The scheme is shown below.

반응식1Scheme 1

전구체인 2,7-디브로모플로렌에 염기인 포타시움터셔리부톡사이드 하에 벤조페논과 5시간동안 반응시키면 단량체 2,7-디브로모-9,9'-디벤질리데닐플로렌을 얻을 수 있다. 위에서 만들어진 새로운 단량체와 기존에 알려져있는 2,7-디브로모-9-벤질리데닐플로렌, 또는 2,7-디브로모 9,9-디알킬플로렌과의 공중합을 통하여 고분자를 얻을 수 있고 여기에 말단기로 2-브로모플로렌을 사용한다. 합성된 고분자에 강염기인 포타시움텨셔리부톡사이드를 사용하여 말단기의 9번위치에 있는 수소을 제거하여 탄소음이온을 만든다음 여기에 여러 무기금속과 반응시켜 유무기 복합 전계발광 고분자를 얻을 수 있다. 과정은 반응식2에 나타내었다.When the precursor 2,7-dibromoflorene is reacted with benzophenone for 5 hours under a base potassium tertiary butoxide, a monomer 2,7-dibromo-9,9'-dibenzylideneylfluorene can be obtained. . Polymers can be obtained by copolymerization with the new monomers made above and 2,7-dibromo-9-benzylideneylfluorene or 2,7-dibromo 9,9-dialkylfluorene. 2-bromoflorene is used here as the end group. Potassium butylbutoxide, which is a strong base, is used in the synthesized polymer to remove hydrogen at position 9 of the terminal group to form a carbon anion, and then react with various inorganic metals to obtain an organic-inorganic composite electroluminescent polymer. The procedure is shown in Scheme 2.

반응식2Scheme 2

상기 반응식2에서 R은 알킬기(부틸기,헥실기,옥틸기,등 탄소수가1~22개)이고 X는 페닐기,알킬기 또는 수소이다.그리고 M은 무기금속으로써 Eu, Pd, Sn, Ir, Zn, Cu, Ag, Pt, Ni, Au등이다.In Scheme 2, R is an alkyl group (butyl group, hexyl group, octyl group, etc., 1 to 22 carbon atoms), X is a phenyl group, an alkyl group or hydrogen, and M is an inorganic metal, and Eu, Pd, Sn, Ir, Zn , Cu, Ag, Pt, Ni, Au and the like.

이하, 실시예를 참조로 본 발명을 더욱 상세히 설명하나 본 발명의 범위와 정신은 특허청구범위로부터 벗어나지 않는 한 이들 실시예 범위로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope and spirit of the present invention is not limited to these Examples unless the scope of the claims.

실시예 1Example 1

단량체합성Monomer Synthesis

2,7-디브로모-9,9'-디벤질리데닐플로렌의 합성Synthesis of 2,7-dibromo-9,9'-dibenzylideneylfluorene

온도계와 미케니컬 스터러 및 환류 콘덴스가 부착된 100밀리리터들이 3구 플라스크에 질소 분위기하에서 2,7-디브로모플로렌 1그램과 0.55그램의 벤조페논을 넣고 터셔리부틸알콜 15밀리리터에 녹이고, 0.34그램의 포타시움터셔리부톡사이드 넣고 반응온도를 서서히 올려 5시간 동안 환류시킨다. 반응이 끝나면 실온으로 냉각시키고 메틸렌클로라이드로 3회 추출하고 물로 여러 번 세척하여 무수 황산 마그네슘으로 건조시키고 용매를 진공으로 제거시키면 노란색의 고체가 형성되는데 이를 실리카겔 컬럼으로 정제한 후 다시 용매를 날려보내면 순수한 고체가 얻어진다. 이를 30℃의 진공 오븐에서 충분히 건조시켜 무게를 측정한 결과 수득율은 70% 얻었으며 GC/MS m/e 488(M+) 1H-NMR (CDCl3) δ 6.68(d), 7.25-7.5 (m) 13C-NMR(CDCl3) δ 120 - 148 (12개 peak)100 milliliters with thermometer, mechanical stirrer and reflux condensation were dissolved in 15 milliliters of tertiary butyl alcohol in a three-necked flask with 1 gram of 2,7-dibromofluorene and 0.55 grams of benzophenone under nitrogen atmosphere. Put 0.34 grams of potashitarium butoxide and slowly raise the reaction temperature to reflux for 5 hours. After the reaction, the reaction mixture was cooled to room temperature, extracted three times with methylene chloride, washed several times with water, dried over anhydrous magnesium sulfate, and the solvent was removed in vacuo. A yellow solid was formed, which was purified by a silica gel column, followed by blowing the solvent again. A solid is obtained. The resultant was dried in a vacuum oven at 30 ° C. and weighed. The yield was 70%. GC / MS m / e 488 (M +) 1 H-NMR (CDCl 3 ) δ 6.68 (d), 7.25-7.5 (m ) 13 C-NMR (CDCl3) δ 120-148 (12 peaks)

실시예 2Example 2

중합체의 합성 Synthesis of Polymer

2,7-디브로모-9,9'-디헥실플로렌과 2,7-디브로모-9,9'-디벤질리데닐플로렌의 공중합(C-1)Copolymerization of 2,7-dibromo-9,9'-dihexyl florene with 2,7-dibromo-9,9'-dibenzylideneylfluorene (C-1)

질소 분위기 하에서 교반기가 있는 100밀리리터들이 3구 플라스크에 0.13그램(1밀리몰) 니켈클로라이드와 2.03그램(31밀리몰)의 아연, 2.0그램(7.6밀리몰)의 트리페닐포스핀, 0.156그램(1밀리몰)의 2,2-디피리딜을 넣고 40℃로 가열 후 DMF용매 넣고 90℃로 온도를 올려 활성화시킨 뒤 용액이 적갈색을 띠면 2,7-디브로모-9,9'-디헥실플로렌 2그램(4밀리몰)과 2,7-디브로모-9-디벤질리데닐플로렌 0.49그램(1밀리몰)을 DMF 10밀리리터에 녹여 넣고 톨루엔 10밀리리터 넣고 80℃로 72시간동안 반응시킨다. 말단기로 2-브로모플로렌 0.25그램(1밀리몰)넣고 12시간 반응시킨다. 반응이 완결되면 반응물을 증류수와 염산으로 씻은 다음 필터를 하고 메틸렌클로라이드로 추출하여 용매를 완전히 날린 후 노란색의 고체를 얻었다.In a 100 milliliter three-necked flask with a stirrer in a nitrogen atmosphere, 0.13 grams (1 mmol) nickel chloride and 2.03 grams (31 mmol) zinc, 2.0 grams (7.6 mmol) triphenylphosphine, 0.156 grams (1 mmol) Add 2,2-dipyridyl, heat to 40 ℃, activate DMF solvent, raise the temperature to 90 ℃, and activate the solution. When the solution is reddish brown, 2 grams of 2,7-dibromo-9,9'-dihexylfluorene ( 4 mmol) and 0.49 grams (1 mmol) of 2,7-dibromo-9-dibenzylideneylfluorene are dissolved in 10 milliliters of DMF, and 10 milliliters of toluene are added and reacted at 80 ° C for 72 hours. 0.25 g (1 mmol) of 2-bromoflorene as a terminal group was added and reacted for 12 hours. When the reaction was completed, the reaction was washed with distilled water and hydrochloric acid, filtered and extracted with methylene chloride to completely blow off the solvent to give a yellow solid.

실시예 3(C-2)Example 3 (C-2)

2,7-디브로모-9,9'-디헥실플로렌과 2,7디브로모-9,9'-디벤질리데닐플로렌의 공중합체와 EuCl2 와의 반응Reaction of 2,7-dibromo-9,9'-dihexyl florene with a copolymer of 2,7 dibromo-9,9'-dibenzylideneylfluorene and EuCl 2

질소분위기하에서 교반기가 있는 100밀리리터 3구 플라스크에 0.5그램 2,7-디브로모-90.5 gram 2,7-Dibromo-9 in a 100 milliliter three-necked flask with agitator under nitrogen atmosphere

,9'-디헥실플로렌과 2,7디브로모-9-디벤질리데닐플로렌의 공중합체을 넣고 THF 20밀리리터 넣고 포타시움터셔리부톡사이드 0.4그램넣고 30분간 교반시킨다. 그 다음 EuCl2 0.5그램 넣고 1시간 환류시킨다. 반응이 완결된 후 증류수에 반응물을 넣고 교반시켜 준 다음 메틸렌클로라이드로 추출한다. 용매를 완전히 날린 후 빨간색의 고체를 얻었다.A copolymer of 9'-dihexyl fluorene and 2,7 dibromo-9-dibenzylideneyl fluorene was added, 20 milliliters of THF was added, and 0.4 g of potashium butoxide was stirred for 30 minutes. Then add 0.5 grams of EuCl 2 and reflux for 1 hour. After the reaction was completed, the reactant was added to distilled water, stirred and extracted with methylene chloride. The solvent was blown off completely to give a red solid.

실시예 4Example 4

광발광특성Photoluminescence Characteristics

도1에는 실시예 1의 단량체의 수소 핵자기공명 스펙트럼을 나타내었으며 도2에는 실시예 2(C-1)와 실시예 3(C-2)의 공중합체 광발광(Photoluminescence, 이하 PL) 스펙트럼을 나타내었다.Figure 1 shows the hydrogen nuclear magnetic resonance spectrum of the monomer of Example 1 and Figure 2 shows a photoluminescence (PL) spectrum of the copolymer of Example 2 (C-1) and Example 3 (C-2) Indicated.

본 발명의 단량체를 이용한 중합체합성과 그 중합체는 발광층의 재료로서 사용될 수 있다. 즉 본 발명의 중합체는 양극/발광층/음극 또는 필요시 여기에 전달층 및 반사층이 포함되도록 구성된 전기발광 소자에 사용될 수 있다. Polymer synthesis using the monomer of the present invention and the polymer can be used as a material of the light emitting layer. That is, the polymer of the present invention can be used in an anode / light emitting layer / cathode or, if necessary, in an electroluminescent device configured to include a transfer layer and a reflective layer.

도1은 본 발명의 실시예 1의 단량체의 수소 핵자기공명 스펙트럼1 is a hydrogen nuclear magnetic resonance spectrum of the monomer of Example 1 of the present invention

도2는 본 발명의 실시예 2(C-1)와 실시예 3(C-2)의 공중합체의 광발광(Photoluminescence, 이하 PL) 스펙트럼.2 is a photoluminescence (PL) spectrum of a copolymer of Example 2 (C-1) and Example 3 (C-2) of the present invention.

도3은 본 발명의 실시예에 따른 전계발광 소자의 구성 단면도.3 is a cross-sectional view of a configuration of an electroluminescent device according to an embodiment of the present invention.

도4는 본 발명의 실시예에 따른 전계발광 소자의 발광 사진Figure 4 is a light emission picture of the electroluminescent device according to an embodiment of the present invention

Claims (4)

화학식 1의 구조를 갖는 단량체와 그 단량체가 포함된 중합체Monomer having the structure of Formula 1 and polymer containing the monomer 제 1항에 있어서 말단기에 무기금속( Eu, Pd, Sn, Ir, Zn, Cu, Ag, Pt, Ni, Au등)이 결합된 형태가 특징인 중합체 The polymer according to claim 1, wherein an inorganic metal (Eu, Pd, Sn, Ir, Zn, Cu, Ag, Pt, Ni, Au, etc.) is bonded to the terminal group. 제 1항에 있어서 상기 중합체를 이루는 단량체 반복단위가 서로 동일한 동 종중합체이거나 또는 서로 상이한 공중합체인 것이 특징인 중합체The polymer according to claim 1, wherein the monomer repeating units forming the polymer are the same homopolymers or different copolymers. 제 1항 내지 제 4항 중 어느 한 항의 중합체를 발광층으로 함유하는 전기발 Electrophoresis containing the polymer of any one of Claims 1-4 as a light emitting layer 광 소자Optical element
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