KR100415986B1 - Manufacturing method of block copolymers of ruthenium complex-comprising methacrylate - Google Patents

Abstract

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

Manufacturing method of ruthenium complex containing methacrylate block copolymer {MANUFACTURING METHOD OF BLOCK COPOLYMERS OF RUTHENIUM COMPLEX-COMPRISING METHACRYLATE}

The present invention relates to a ruthenium complex-containing methacrylate block copolymer by anionic polymerization and a method for producing the same.

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.

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.

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.

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].

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.

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].

The present invention has been invented to solve the problems progressed in the conventional organic light emitting polymer.

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.

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.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to this configuration.

1 is a TGA diagram showing the thermal properties of the ruthenium complex-containing block copolymer of the present invention,

2 is a view showing the light absorption characteristics of the ruthenium complex-containing block copolymer of the present invention,

3 is a view showing the luminescence properties of the ruthenium complex-containing block copolymer of the present invention.

Synthesis of 2- (N-carbazolyl) ethyl methacrylate

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.

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).

Analysis of the monomers was confirmed using ¹ H-NMR, ¹³ C-NMR and FT-IR.

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.

Polymerization of Block Copolymers (PCzMA-b-P2VP-b-PCzMA)

All reactions were polymerized using a glass apparatus under high vacuum and THF was used as the solvent.

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.

After the reaction was completed, freeze drying was performed to obtain (PCzMA-b-P2VP-b-PCzMA).

Thus synthesized polymer was measured by gel permeation chromatography (GPC) to determine the molecular weight and molecular weight distribution.

Ru (trpy) (bpy) Cl ₂ Manufacture

This is to prepare a ruthenium containing block copolymer together with the above polymer PCzMA-b-P2VP-b-PCzMA.

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 .

Preparation of Rudenium-containing Block Copolymer

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.

Rudnium-containing PCzMA- b -P2VP- b Scheme of Preparation of -PCzMA Block Polymer

¹ H-NMR and UV / VIS spectroscopy were used to analyze the complex formation between the block copolymer and ruthenium.

^{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.

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).

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.

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. .

1 shows a TGA diagram which is one of the thermal analysis instruments.

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.

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.

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.

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.

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.

Table 1 below shows the results of making the polymer 2- (N-carbazolyl) ethyl methacrylate (CzMA) at −78 ° C. (Examples 1-6).

Example Number Amount of reagent (mmol) 2VP / I CzMA / 2VP yield(%) Mn Mn / Mw ^d K-Naph DPE 2VP CzMA Calculated ^a NMR ^b Calculated ^c Measurement ^d 123456 0.0960.1020.1070.1020.1280.103 0.1170.1380.1290.1380.1380.129 -0.1090.3000.5050.9181.038 2.8552.2022.1002.2232.2202.372 -1.072.804.957.1710.08 -20.207.004.402.422.29 ^-e - ^e 4.502.582.39 100100100100100100 16,00012,50012,00013,50011,50015,500 15,00013,50010,00013,00011,50013,500 1.091.091.091.101.071.07 a is CzMA / 2VP, b is the result measured by ¹ H-NMR, and c is Mn = {(zMA / K-Naph) x 2 x Mw of CzMA + + (2VP / K-Naph) x 2 x MV} of 2VP + MW × 2 of DPE, d is a value measured by SEC using a polymethyl methacrylate (PMMA) standard, and e could not be measured by ¹ H-NMR.

As shown in Table 1, the amount of CzMA

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.

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.

Claims (8)

delete delete delete delete Ruthenium complex-containing poly ((2-N-carbazolyl) ethyl methacrylate) -block-poly (2-vinylpyridine) -block-poly having the following formula (I), consisting of the following steps by anionic polymerization: Process for preparing ((2-N-carbazolyl) ethylmethacrylate) (PCzMA- b- P2VP- b- PCzMA block) copolymer: i) Diphenylethylene dissolved in tetrahydrofuran was added to the potassium-naphthalene initiator to react, followed by addition of 2-vinylpyridine (2VP), followed by (2-N-carbazolyl) ethyl methacryl The reaction was terminated by adding methanol (CzMA), followed by freeze drying to form a PCzMA- b -P2VP- b -PCzMA block copolymer having the following structural formula (II) having carbazole as a side chain. Obtained, and Ru (trpy) (bpy) Cl ₂ having the following structural formula (III) was dissolved in chloroform, and then refluxed by adding triethylamine as a reducing agent, Ii) The reaction is cooled to room temperature, then dissolved in tetrahydrofuran and filtered, the unmelted components are removed, and only the molten portion is dried to obtain a block copolymer containing a rudenium complex. Structural Formula (Ⅰ) Structural Formula (Ⅱ) Structural Formula (Ⅲ) 6. The method of claim 5 wherein Ru (trpy) (bpy) Cl ₂ attaches to 2-PV of the PCzMA- b- P2VP- b- PCzMA block copolymer. 6. The method of claim 5, wherein Ru (trpy) (bpy) Cl ₂ is formed by the coordinating bond of terpyridine and bipyridine. delete