KR100415986B1 - Manufacturing method of block copolymers of ruthenium complex-comprising methacrylate - Google Patents
Manufacturing method of block copolymers of ruthenium complex-comprising methacrylate Download PDFInfo
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Abstract
본 발명은 루데늄 함유 PCzMA-b-P2VP-b-PCzMA 블록 공중합체에 있어서, Ru(trpy)(bpy)(2VP)의 함량에 따라 흡광 특성, 발광 특성 및 에너지 전달 현상을 나타내는 것을 특징으로 하는 루데늄 함유 PCzMA-b-P2VP-b-PCzMA 블록 공중합체에 관한 것이다.In the ruthenium-containing PCzMA- b -P2VP- b -PCzMA block copolymer, the absorption characteristics, the luminescence properties and the energy transfer phenomena are exhibited according to the Ru (trpy) (bpy) (2VP) content. A rudennium-containing PCzMA- b -P2VP- b -PCzMA block copolymer.
Description
본 발명은 음이온 중합에 의한 루데늄 착체 함유 메타아크릴레이트계 블록 공중합체 및 이의 제조 방법에 관한 것이다.The present invention relates to a ruthenium complex-containing methacrylate block copolymer by anionic polymerization and a method for producing the same.
더욱 구체적으로, 본 발명은 카르바졸을 측쇄로 갖는 2-(N-카르바졸릴)에틸 메타아크릴레이트와 2-비닐피리딘과의 음이온 중합에 의한 PCzMA-b-P2VP-b-PCzMA 블록 공중합체, 및 루데늄 착체 함유 PCzMA-b-P2VP-b-PCzMA 블록 공중합체에 관한것이고, 또한 분자량 및 분자량 분포가 조절된 블록 공중합체에 있어서의 블록 공중합체의 한 블록의 크기의 변화에 따른 광학 성질에 관한 것이다. 상기에서 "광학 활성"이라 함은 흡광성 및 발광성을 의미한다.More specifically, the present invention relates to a PCzMA- b- P2VP- b- PCzMA block copolymer obtained by anionic polymerization of 2-vinylpyridine with 2- (N-carbazolyl) ethyl methacrylate having a carbazole as a side chain, And a ruthenium complex-containing PCzMA- b- P2VP- b- PCzMA block copolymer, and also to optical properties according to the change in the size of one block of the block copolymer in a block copolymer having controlled molecular weight and molecular weight distribution. It is about. The term "optical activity" as used herein means absorbance and luminescence.
또한, 이러한 발광 현상 연구에 따라, 분자간의 에너지 전달이 우수하면 발광성이 증진되고, 분자간의 에너지 전달이 열등하면 발광 특성은 저하되는 현상에 대한 연구도 본 발명에 포함된다.In addition, according to the light emission phenomenon, the present invention also includes a study on the phenomenon that the light emission property is enhanced when the energy transfer between the molecules is excellent, and the light emission characteristics are lowered when the energy transfer between the molecules is inferior.
카르바졸을 갖는 물질은 광전도성, 광굴절성 및 비선형 광학 물질로서 널리 사용되고 있으며, 최근에 이를 이용한 발광성 물질의 매체로서 사용하는 논문이 공지되어 있다[(1) Y. Zhang, T. Wada, and H. Sasabe,Chem. Commun.,1996, 621. (2) Y. Zhang, T. Wada, and H. Sasabe,Macromol. Chem. Phys.,1996,197, 667. (3) K. Tamura, A. B. Padias, H. K. Hall Jr., and N. Peyghambarian,Appl. Phys. Lett.,1992,60, 1803].Carbazole-containing materials are widely used as photoconductive, photorefractive and nonlinear optical materials, and recently, a paper using them as a medium for luminescent materials is known [(1) Y. Zhang, T. Wada, and H. Sasabe, Chem. Commun. , 1996 , 621. (2) Y. Zhang, T. Wada, and H. Sasabe, Macromol. Chem. Phys. , 1996 , 197 , 667. (3) K. Tamura, AB Padias, HK Hall Jr., and N. Peyghambarian, Appl. Phys. Lett. , 1992 , 60 , 1803.
또한, 카르바졸과 금속 착체를 아세틸렌으로 서로 연결하여 분자내의 에너지 전달 현상을 연구한 예도 공지되어 있다[A. Ribou, T. Wada, and H. Sasabe,Inorganica Chemica Acta,1999,288, 134].In addition, examples of linking carbazole and metal complexes with acetylene to study energy transfer in the molecule are also known [A. Ribou, T. Wada, and H. Sasabe, Inorganica Chemica Acta , 1999 , 288 , 134].
메타아크릴레이트에 대한 음이온 중합은 많은 연구가 진행되었으나 중합 중에 많은 부반응이 발생하기 때문에 이를 해결하기 위한 연구가 세계적으로 진행되고 있는 실정이다.Although many studies have been conducted on anion polymerization to methacrylates, many side reactions occur during polymerization, and thus, studies to solve this problem are being conducted worldwide.
그 대표적인 예로서, 중합 중에 첨가제를 도입함으로써 첨가제가 단량체와 착체를 형성하는 현상을 이용하여 부반응을 최소화하는 연구가 진행되고 있다 [H.Ozaki, A. Hirao, S. Nakahama,Macromol. Chem. Phys.,1995,196, 2099; T. Ishizone, K. Yoshimura, E. Yanase, S.Nakahama,Macromolecules,1999,32, 955; 카르바졸을 측쇄로 갖는 메타아크릴레이트 유도체의 음이온 중합, 조영선, 이재석, 대한민국특허출원].As a representative example, research is being conducted to minimize side reactions by introducing additives during polymerization to form complexes with monomers [H. Ozaki, A. Hirao, S. Nakahama, Macromol. Chem. Phys ., 1995 , 196 , 2099; T. Ishizone, K. Yoshimura, E. Yanase, S. Nakahama, Macromolecules , 1999 , 32 , 955; Anionic Polymerization of Methaacrylate Derivatives Having Carbazole as Side Chain, Cho Young-sun, Lee Jae-seok, Korea Patent Application].
본 발명은 종래의 유기 발광 중합체에서 진행되는 문제점을 해결하기 위하여 발명된 것이다.The present invention has been invented to solve the problems progressed in the conventional organic light emitting polymer.
본 발명은 2-(N-카르바졸릴)에틸 메타아크릴레이트의 함량을 일정하게 유지하고 2-비닐피리딘의 함량을 조절하여 중합한, 조절된 분자량과 분자량 분포를 갖는 루데늄 착제 함유 블록 공중합체 및 이의 제조 방법에 관한 것이고, 또한, 상기 블록 공중합체의 흡광 및 발광 특성과, 이에 따른 분자간의 에너지 전달에 관한 것인데, 상기의 루데늄 함유 블록 공중합체의 제조에 있어서, 터피리딘(terpyridin)과 바이피리딘(bipyridin)를 이용한 루데늄 착체는 함량이 조절된 2-비닐피리딘에 부착되고, 흡광 및 발광 특성은 부착된 루데늄 착체의 함량에 따른다.The present invention relates to a ruthenium complex-containing block copolymer having a controlled molecular weight and molecular weight distribution polymerized by maintaining a constant content of 2- (N-carbazolyl) ethyl methacrylate and controlling the content of 2-vinylpyridine. And to a method for preparing the same, and also to light absorption and luminescence properties of the block copolymer and energy transfer between molecules according to the present invention. Ruthenium complexes using bipyridin are attached to 2-vinylpyridine with a controlled content, and absorption and luminescence properties depend on the content of the attached rudenium complex.
상기 목적에 따라, 본 발명은 카르바졸을 측쇄로 갖는 2-(N-카르바졸릴)에틸 메타아크릴레이트 단량체와 2-비닐피리딘의 블록 공중합체 및 이의 제조 방법; 상기 블록 공중합체와, 터피리딘과 바이피리딘이 배위결합을 형성하고 있는 루데늄 착체를 이용한 루데늄 함유 블록 공중합체 및 이의 제조 방법; 및 상기 블록 공중합체의 흡광 및 발광 특성을 제공한다.In accordance with the above object, the present invention provides a block copolymer of 2- (N-carbazolyl) ethyl methacrylate monomer having 2-carbazole as a side chain and 2-vinylpyridine and a method for producing the same; A ruthenium-containing block copolymer using the ruthenium complex in which the block copolymer, terpyridine and bipyridine form a coordinating bond, and a method for producing the same; And absorbance and luminescence properties of the block copolymer.
이하에서, 본 발명을 상세히 설명한다. 하지만 본 구성내용에 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail. However, the present invention is not limited to this configuration.
도1은 본 발명의 루데늄 착체 함유 블록 공중합체의 열적 성질을 보여주는 TGA 도면이고,1 is a TGA diagram showing the thermal properties of the ruthenium complex-containing block copolymer of the present invention,
도2는 본 발명의 루데늄 착체 함유 블록 공중합체의 흡광 특성을 보여주는 도면이며,2 is a view showing the light absorption characteristics of the ruthenium complex-containing block copolymer of the present invention,
도3은 본 발명의 루데늄 착체 함유 블록 공중합체의 발광 특성을 보여주는 도면이다.3 is a view showing the luminescence properties of the ruthenium complex-containing block copolymer of the present invention.
2-(N-카르바졸릴)에틸 메타아크릴레이트의 합성Synthesis of 2- (N-carbazolyl) ethyl methacrylate
카르바졸(50g)을 에탄올을 이용하여 재결정한 후, 디메틸포름아미드(DMF, 100ml)에 용융시키고, 여기에 NaH(40g)와 에틸렌카보네이트(80g)를 첨가하여 60℃에서 12시간 반응시켰다. 반응 완료 후, 물에 침전시켜 여과했다. 여과된 백색 고체를 에탄올로 용융시키고, 비용융 부분을 여과 제거했다. 고체를 여과한 후, 에탄올 용액을 건조시켜 9-(히드록시에틸)카르바졸을 얻었다.Carbazole (50 g) was recrystallized with ethanol, and then melted in dimethylformamide (DMF, 100 ml), and NaH (40 g) and ethylene carbonate (80 g) were added thereto and reacted at 60 ° C for 12 hours. After the reaction was completed, the precipitate was precipitated in water and filtered. The filtered white solid was melted with ethanol and the non-melted portion was filtered off. After filtering off the solid, the ethanol solution was dried to give 9- (hydroxyethyl) carbazole.
그 다음, 9-(히드록시에틸)카르바졸(50g)을 테트라히드로푸란(THF, 100ml)에 녹이고, 메타크릴산(50ml)을 첨가하고, 여기에 촉매로서 디시클로헥실카보디이미드(50g)와 디메틸아미노피리딘(25g)을 첨가하여 0 ℃에서 5시간 동안 반응시켰다. 반응 완료 후, 침전된 염을 여과 제거하고 잔류 용액의 THF를 제거하고 에탄올에서 재결정하여 순수한 2-(N-카르바졸릴)에틸 메타아크릴레이트(CzMA)를 얻었다.Then, 9- (hydroxyethyl) carbazole (50 g) was dissolved in tetrahydrofuran (THF, 100 ml), methacrylic acid (50 ml) was added, and dicyclohexylcarbodiimide (50 g) was added as a catalyst. And dimethylaminopyridine (25 g) were added and reacted at 0 ° C. for 5 hours. After completion of the reaction, the precipitated salt was filtered off, the THF of the remaining solution was removed and recrystallized from ethanol to obtain pure 2- (N-carbazolyl) ethyl methacrylate (CzMA).
단량체의 분석은1H-NMR,13C-NMR 및 FT-IR을 이용하여 확인하였다.Analysis of the monomers was confirmed using 1 H-NMR, 13 C-NMR and FT-IR.
한편, 2-비닐피리딘(2VP)을 진공 하에서 증류하고, MgSO4를 첨가하여 12시간 동안 반응시켜 잔류 수분을 제거한 후, 고(高)진공 하에서 다시 증류했다. 또한, 중합 중에 반응성을 낮추기 위해서 사용하는 디페닐에틸렌(DPE)을 NaOH로 세척하고, 진공 하에서 증류한 후, 고진공 하에서 다시 증류했다.On the other hand, 2-vinylpyridine (2VP) was distilled under vacuum, MgSO 4 was added and reacted for 12 hours to remove residual water, followed by distillation again under high vacuum. In addition, diphenylethylene (DPE) used for lowering reactivity during polymerization was washed with NaOH, distilled under vacuum, and then distilled under high vacuum.
블록 공중합체(PCzMA-b-P2VP-b-PCzMA)의 중합Polymerization of Block Copolymers (PCzMA-b-P2VP-b-PCzMA)
모든 반응은 고진공 하에서 유리로 된 장치를 이용하여 중합하였으며 용매로는 THF를 사용하였다.All reactions were polymerized using a glass apparatus under high vacuum and THF was used as the solvent.
개시제인 칼륨-나프탈렌 (K-Naph)의 반응성을 낮추기 위해 THF에 녹아있는 DPE를 K-Naph 에 첨가하여 -78℃에서 30분 동안 반응시킨 후, 2VP를 첨가하여 -78℃에서 4시간 동안 반응시켰다. 여기에 CzMA를 첨가하고, -78℃에서 4시간 동안 반응시킨 후, 메탄올을 첨가하여 반응을 종료하였다.To reduce the reactivity of the initiator potassium-naphthalene (K-Naph), DPE dissolved in THF was added to K-Naph and reacted at -78 ° C for 30 minutes, followed by 2VP at -78 ° C for 4 hours. I was. CzMA was added thereto and reacted at −78 ° C. for 4 hours, and then methanol was added to terminate the reaction.
반응 종료 후, 냉동 건조하여 (PCzMA-b-P2VP-b-PCzMA)를 얻었다.After the reaction was completed, freeze drying was performed to obtain (PCzMA-b-P2VP-b-PCzMA).
이렇게 합성된 중합체는 겔투과 크로마토그래피(GPC)로 측정하여 분자량과 분자량 분포를 측정하였다.Thus synthesized polymer was measured by gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution.
Ru(trpy)(bpy)ClRu (trpy) (bpy) Cl 22 의 제조Manufacture
이는 상기의 중합체 PCzMA-b-P2VP-b-PCzMA 와 함께 루데늄 함유 블록 공중합체를 제조하기 위한 것이다.This is to prepare a ruthenium containing block copolymer together with the above polymer PCzMA-b-P2VP-b-PCzMA.
RuCl3ㆍH2O (0.56 g)와 터피리딘 (trpy, 0.50 g)을 에탄올에 녹여서 3시간 동안 환류시켰다. 3시간 후에 온도를 상온으로 내려서 여과한 다음, 여과된 고체를 에탄올과 에테르로 세척하여 RuⅢ(trpy)Cl3를 얻고, 이에 바이피리딘(bpy, 2.12 g)을 첨가하고 클로로포름(CHCl3)으로 용융시키고, 여기에 트리에틸아민을 환원제로 첨가하여 90분 동안 환류시킨다. 반응물을 상온으로 낮춘 다음, THF에 용융시켜 여과하고 용융된 성분을 제거하고, 용융되지 않은 부분만 건조시켜 Ru(trpy)(bpy)Cl2를 얻었다.RuCl 3 H 2 O (0.56 g) and terpyridine (trpy, 0.50 g) were dissolved in ethanol and refluxed for 3 hours. After 3 hours, the temperature was lowered to room temperature and filtered, and then the filtered solid was washed with ethanol and ether to obtain Ru III (trpy) Cl 3, to which bipyridine (bpy, 2.12 g) was added, followed by chloroform (CHCl 3 ). Melt and add triethylamine as reducing agent to reflux for 90 minutes. After the reaction was cooled to room temperature, it was dissolved in THF, filtered, and the molten component was removed, and only the unmelted portion was dried to obtain Ru (trpy) (bpy) Cl 2 .
루데늄 함유 블록 공중합체를 제조Preparation of Rudenium-containing Block Copolymer
상기의 중합체 PCzMA-b-P2VP-b-PCzMA 및 Ru(trpy)(bpy)Cl2를 클로로포름에 용융시키고, 여기에 환원제로서 트리에틸아민을 첨가하여 90분 동안 환류시킨다. 반응물을 상온으로 낮춘 다음, THF에 용융시켜 여과하고 비용융된 성분을 제거하고, 용융된 부분만 건조시켜 루데늄이 함유된 중합체를 얻는다.The polymers PCzMA- b- P2VP- b- PCzMA and Ru (trpy) (bpy) Cl 2 are melted in chloroform and refluxed for 90 minutes by adding triethylamine as reducing agent. The reaction is cooled to room temperature, then dissolved in THF, filtered, the unmelted components are removed, and only the molten portion is dried to obtain a rudenium-containing polymer.
루데늄 함유 PCzMA-Rudnium-containing PCzMA- bb -P2VP--P2VP- bb -PCzMA 블록 중합체의 제조 도식Scheme of Preparation of -PCzMA Block Polymer
블록 공중합체와 루데늄과의 착체 형성을 분석하기 위해서1H-NMR과 UV/VIS 분광기를 이용하였다. 1 H-NMR and UV / VIS spectroscopy were used to analyze the complex formation between the block copolymer and ruthenium.
1H-NMR 스펙트럼에서는 6.3∼6.6ppm에서 나타나던 PCzMA-b-P2VP-b- PCzMA 에서 2VP 피크가 없어지고 8.7ppm에서 새로운 피크가 나타나고, 중합체에는 없던 피크인 Ru(trpy)(bpy) 피크가 6.6, 7.5 및 8.2 ppm 에서 발견되는 것으로 보아 PCzMA-b-P2VP-b-PCzMA에 루테늄이 성공적으로 붙은 것을 확인할 수 있다. In the 1 H-NMR spectrum, the 2VP peak disappeared at PCzMA- b -P2VP- b -PCzMA, which appeared at 6.3 to 6.6 ppm, the new peak appeared at 8.7 ppm, and the Ru (trpy) (bpy) peak, which was not present in the polymer, was 6.6. The discovery of ruthenium on PCzMA- b -P2VP- b -PCzMA was confirmed to be found at, 7.5 and 8.2 ppm.
합성된 중합체는1H-FT-NMR (Fourier Transform Nuclear Magnet Resornance), FT-IR (Fourier Transform Infrared Spectroscopy), DSC (Differentail Scanning Calorimeter) 및 TGA (Thermogravimetry Analyser)를 이용하여 분석하였다.The synthesized polymer was analyzed using 1 H-FT-NMR (Fourier Transform Nuclear Magnet Resornance), FT-IR (Fourier Transform Infrared Spectroscopy), DSC (Differentail Scanning Calorimeter) and TGA (Thermogravimetry Analyser).
1H NMR (CDCl3) 8.4-7.8 (b, 4H, aromatic), 7.8-6.6 (b, 7H, aromatic), 6.6-6.3 (b, 1H, pyridine), 4.6-3.8 (b, 4H, CH2CH2), 1.2-2.0 (b, 3H, CH3), 0.0-0.5 (b, 2H, CH2-C); IR (KBr, cm-1) 1740 (C=O); Tg115 ℃; Td293 ℃. 1 H NMR (CDCl 3 ) 8.4-7.8 (b, 4H, aromatic), 7.8-6.6 (b, 7H, aromatic), 6.6-6.3 (b, 1H, pyridine), 4.6-3.8 (b, 4H, CH 2 CH 2 ), 1.2-2.0 (b, 3H, CH 3 ), 0.0-0.5 (b, 2H, CH 2 -C); IR (KBr, cm −1 ) 1740 (C═O); T g 115 ° C; T d 293 ° C.
또한, PCzMA-b-P2VP-b-PCzMA 의 2VP는 물과 잘 결합하기 때문에 물의 함량을 조사하여 P2VP의 함량을 계산할 수 있고, 또한 P2VP는 내화성이 있는 것으로 알려져 있기 때문에 이를 이용해 함량을 계산할 수 있다.In addition, since 2VP of PCzMA- b -P2VP- b -PCzMA binds well with water, the content of P2VP can be calculated by examining the water content, and since P2VP is known to be fireproof, the content can be calculated using this. .
도1는 열분석 기구의 하나인 TGA 도면을 나타낸 것이다.1 shows a TGA diagram which is one of the thermal analysis instruments.
도1에서 보는 바와 같이, 초기 100 ℃ 부근에서 무게 감소는 P2VP 에 결합한 물에 의한 것이고, 400℃ 이상에서 무게 감소의 형태가 변하는 것은 P2VP의 내화성 때문이다. 초기 물에 의한 무게 감소는 0.5 내지 3.0% 정도인데, 이는 P2VP에 부착가능한 물의 함량과 유사하고, 또한 400℃ 이상에서 남아있는 무게도 P2VP의 함량과 일치함을 알 수 있다.As shown in Figure 1, the weight loss near the initial 100 ℃ is due to the water bound to P2VP, the change in the form of weight loss above 400 ℃ is due to the fire resistance of P2VP. The weight loss by the initial water is about 0.5 to 3.0%, which is similar to the content of water attachable to P2VP, and it can be seen that the weight remaining above 400 ° C. is also consistent with the content of P2VP.
도2는 UV/VIS 스펙트럼을 나타낸 것으로서, PCzMA-b-P2VP-b-PCzMA의 피크는 290nm, 320nm, 및 340 nm에서 발견되는데, 이는 2-비닐피리딘과 카르바졸에서 나타나는 흡수 피크이다. Ru(trpy)(bpy)Cl2에서는 bpy 및 trpy의 흡수 최대 피크가 293nm 및 320nm에서 나타나고, 루데늄과 리간드(bpy, trpy)사이의 전하 이동 현상에 의해서 나타나는 피크가 509 nm 에서 흡수 최대 피크를 보여주고 있다. 그러나, PCzMA-b-P2VP-b-PCzMA에 루데늄을 붙인 중합체의 경우에는 루데늄과 리간드(bpy, trpy, 2VP)사이의 전하 이동 현상에서 나타나는 피크가 410 nm에서 흡수 최대 피크가 나타난다. 이로써, PCzMA-b-P2VP-b-PCzMA에 루데늄이 착체를 형성하는 것을 확인할 수 있었다. 또한, 루데늄 착체의 함량이 증가함에 따라 410 nm에서의 흡수 피크가 증가함을 보여주고 있다.Figure 2 shows the UV / VIS spectrum, where the peaks of PCzMA- b -P2VP- b -PCzMA are found at 290 nm, 320 nm, and 340 nm, which are the absorption peaks appearing in 2-vinylpyridine and carbazole. In Ru (trpy) (bpy) Cl 2 , the peaks of absorption peaks of bpy and trpy appear at 293 nm and 320 nm, and the peaks due to the charge transfer phenomenon between rudenium and ligands (bpy, trpy) show the maximum absorption peak at 509 nm. Is showing. However, in the case of the polymer attached to ruthenium to PCzMA-b-P2VP-b-PCzMA, the peak at the charge transfer phenomenon between ruthenium and ligands (bpy, trpy, 2VP) shows an absorption maximum peak at 410 nm. As a result, it was confirmed that ruthenium forms a complex on PCzMA- b- P2VP- b- PCzMA. It is also shown that the absorption peak at 410 nm increases as the content of ruthenium complex increases.
도3은 PCzMA-b-P2VP-b-PCzMA, 및 루데늄 착체의 함량이 다른 루데늄이 착체로 결합한 PCzMA-b-P2VP-b-PCzMA의 발광 특성을 나타내고 있다.3 shows the light emission characteristics of PCzMA- b -P2VP- b -PCzMA coupled into PCzMA- b -P2VP- b -PCzMA, and Lu other base denyum denyum content of the complex complex.
도3에서 보는 바와 같이, PCzMA의 발광 피크는 349nm 및 360nm에서 최대 피크를 보여주고 있으며, 루데늄이 착체로 결합된 블록 공중합체의 경우는 466 nm에서 최대 발광 피크를 보인다. 최대 발광 피크가 346nm 및 360nm에서 466nm로 이동한 것은 카르바졸을 함유하는 블록에서 루데늄을 함유하는 블록으로 에너지의 전달 현상에 의한 것이다. 또한, 466 nm에서의 발광 피크가 루데늄 착체의 함량이 증가함에 따라 증가함을 볼 수 있다. 이에 반해, 카르바졸의 발광 피크의 하나인 360 nm에서의 발광 피크는 줄어듦을 보여주는데, 이는 루데늄의 함량이 증가함에 따라 에너지 전달 현상이 증가함을 보여준다.As shown in FIG. 3, the emission peaks of PCzMA show the maximum peaks at 349 nm and 360 nm, and the maximum emission peak at 466 nm in the case of a block copolymer in which rudenium is complexed. The peak emission peak shifted from 346 nm and 360 nm to 466 nm is due to the transfer of energy from the block containing carbazole to the block containing rudenium. In addition, it can be seen that the emission peak at 466 nm increases with increasing content of the rudenium complex. In contrast, the emission peak at 360 nm, which is one of the emission peaks of carbazole, decreases, indicating that the energy transfer phenomenon increases as the rudenium content increases.
이하에서, 본 발명을 하기의 실시예에 의하여 설명하지만, 실시예에 의해 본발명의 기술적 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described by the following examples, but the technical scope of the present invention is not limited by the examples.
하기의 표1은 단량체 2-(N-카르바졸릴)에틸 메타아크릴레이트 (CzMA)를 -78℃에서 중합체를 만든 결과(실시예 1-6)를 나타낸 것이다.Table 1 below shows the results of making the polymer 2- (N-carbazolyl) ethyl methacrylate (CzMA) at −78 ° C. (Examples 1-6).
표1에서 보는 바와 같이, CzMA의 양As shown in Table 1, the amount of CzMA
은 거의 일정하게 유지되고, 2VP의 양은 사슬당 각각 0, 2, 6, 10, 14 및 20개의 양이 들어가도록 조절하였고, 모든 반응에서 수율은 100% 이고, 부반응이 없이 분자량 분포가 좁고 계산된 분자량과 측정된 분자량이 잘 일치함을 알 수 있다.Is maintained almost constant, and the amount of 2VP is adjusted to contain 0, 2, 6, 10, 14 and 20 amounts per chain, respectively, and the yield is 100% in all reactions, and the molecular weight distribution is narrow and calculated without side reactions. It can be seen that the molecular weight and the measured molecular weight agree well.
본 발명의 루데늄 착체 함유 2-(N-카르바졸릴)에틸 메타아크릴레이트 블록 공중합체에 있어서, 블록 공중합체 중 루데늄 착체의 함량이 증가함에 따라 발광 특성의 변화를 보여 주는데, 이에 따라 발광 특성을 갖는 카르바졸과 루데늄 착체를 이용하여 분자 크기의 조절을 통하여 발광 특성의 변화를 예측할 수 있다.In the ruthenium complex-containing 2- (N-carbazolyl) ethyl methacrylate block copolymer of the present invention, the luminescence properties change as the ruthenium complex content in the block copolymer increases, thereby emitting light. Carbazole and rudenium complexes having properties can be used to predict changes in luminescence properties by controlling molecular size.
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