KR100408233B1 - Novel Organic Light-emitting Polymer and Light-emitting Diode Prepared by Using the Same - Google Patents

Abstract

The present invention relates to an organic light emitting polymer having improved luminous efficiency and an electroluminescent diode manufactured using the same, wherein the organic light emitting polymer of the present invention has the following formula.

In the above formula, R ₁ , R ₂ and R ₃ are each independently an aliphatic linear alkoxy group, an aliphatic branched alkoxy group, or hydrogen, R ₄ is an aliphatic alkyl group having 2 to 14 carbon atoms, R ₅ is hydrogen or an aryl group to be.

Description

Novel Organic Light-emitting Polymer and Light-emitting Diode Prepared by Using the Same

The present invention relates to an organic light emitting polymer, and more particularly, to an organic light emitting polymer having improved luminous efficiency and an electroluminescent diode manufactured using the same.

The semiconductor industry using silicon semiconductors has developed remarkably over the last few decades, and organic semiconductors have also developed remarkably. Recently, due to the development of the optical communication and multimedia fields, optoelectronic materials have become the center of the information communication industry, and display technology has been developed day by day due to the development of information communication. Currently, the liquid crystal display typically used has the advantage of being lighter than the conventional CRT, but has a disadvantage in that a viewing angle is limited and a back light is required. In contrast, a display using an organic light emitting diode (OLED) is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed.

Electroluminescent diodes are classified into inorganic light emitting diodes and organic light emitting diodes. Among them, inorganic light emitting diodes composed of GaN, ZnS, etc. are currently commercially available, but the driving voltage is 200 V (AC) or more, Not only is it difficult, but it is also expensive. In 1987, Eastman Kodak Co. announced a multi-layered organic light emitting diode that emits green light using aluminum complex (Alq ₃ ), an organometallic compound consisting of a conjugated double bond, as a light emitting material by Tang et al. CW Tang et al., Appl. Phys. Lett ., 51: 913 (1987)), said organic light emitting diode has a quantum efficiency (number of quantum coming out / number of injected electrons * 100, external quantum efficiency) This 1% and the luminance was 1000 cd / mm ² . Since then, organic light-emitting diodes with easy color tuning and high quantum efficiency have been developed. However, the developed organic light emitting diode has lower mechanical properties than the conventionally developed light emitting diode, and organic light emitting diodes are rearranged by heat generated during diode operation, resulting in low luminous efficiency and short lifetime of the diode. Has its drawbacks, and efforts to overcome it have continued. In the United Kingdom in 1990, University of Cambridge Friend and the like having a combination of one to some extent solve the drawbacks of the above-described organic light emitting diode conjugated poly (p - phenylenevinylene): electroluminescence with (poly (p -phenylenevinylene), PPV) Since the development of diodes (JH Burroughes et al., Nature , 347: 539 (1990)), research into organic polymers has been actively conducted to develop red, green and blue organic light emitting polymers that emit light in the visible region. A polymer LED (light emitting diode) having a multilayer structure composed of the developed organic light emitting polymer has been developed.

The color of light emitted from the organic light emitting polymer is determined by a band gap, which is a difference between the HOMO and LUMO energy levels, and the driving voltage of the polymer light emitting diode (PLED). Quantum efficiency is determined by the difference between the work function and homo level of the anode injecting holes and the difference between the work function and Lumo energy level of the cathode injecting electrons. The homo level of most organic light emitting polymers is easy to accept holes from the cathode because of the small energy difference from the work function of indium tin oxide (ITO), a typical anode material. Since the hole injection rate (or hole injection amount) and electron injection rate (or electron injection amount) are not balanced, the first injected hole is tunneled to the cathode, resulting in an ohmic current, resulting in quantum efficiency. Is lowered and the lifetime of the diode is shortened due to heat generation. According to the research results published so far, when introducing functional groups such as cyano (CN) and oxadiazole having strong electron affinity into the polymer main chain or side chain to balance the hole and electron injection, It facilitates the injection of electrons and lowers the homogenous level to balance hole injection and electron injection, resulting in improved quantum efficiency but higher operating voltage (NC Greenham et al., Nature 365: 628 (1993), Z. Peng et al., Chem. Mater ., 11: 1138 (1999). In order to overcome this disadvantage, a material having a strong electron affinity is coated with a thin film between the light emitting layer and the anode to form a multi-layer electroluminescent diode (Q. Pei et al., Chem. Mater . 7: 1568 (1995), M. Struk electroluminescent j et al., Science , 267: 1969 (1995), M. Struk electroluminescent j et al., J. Am. Chem. Soc ., 117 : 11976 (1995), K. Kim et al., Synth.Met. , 114: 49 (2000) or by blending materials with strong electron affinity with luminescent materials to increase quantum efficiency (Y. Ohmori et. al., Jpn. J. Appl. Phys. , 35: 4105 (1996), C. Wu et. Al., IEEE Trans. Electroluminescent ectron device , 44: 1269 (1997)), rearrangement or phase separation of space-generating or blended materials As a result, the research to improve the efficiency of the organic light emitting diode has not made much progress.

On the other hand, U.S. Patent No. 5,408,109 discloses a conventional so as to increase the solubility in an organic solvent, poly (p - phenylenevinylene) which the alkyl or alkoxy long-chain introducing the poly in the side chain of the polymer (p - phenylenevinylene) based A polymer is disclosed and US Pat. No. 6,127,693 discloses an organic comprising a blue emitting poly ( p -phenylenevinylene) copolymer and an orange (or red) emitting poly ( p -phenylenevinylene) alkoxy-substituted derivative. A light emitting diode having a light emitting layer is disclosed. In addition, US Pat. No. 6,165,383 discloses anthracene derivatives as precursors for organic light emitting materials and diodes made therefrom.

Throughout this specification, numerous papers and patent documents are referenced and their citations are indicated in parentheses. The disclosures of cited papers and patent documents are incorporated herein by reference in their entirety, and the level of the technical field to which the present invention belongs and the contents of the present invention are explained in more detail.

Accordingly, an object of the present invention is to provide a novel poly ( p -phenylenevinylene) -based organic light emitting polymer that can effectively block the flow of holes.

Another object of the present invention is to provide an electroluminescent diode having a very good quantum efficiency and a low operating voltage.

1 is a schematic diagram showing the structure of a single layer electroluminescent diode using the electroluminescent polymer of the present invention;

2 is a UV-visible spectrum of MPPOXA-PPV and PPOXA-PPV, which is an embodiment of the present invention;

3 is a PL spectrum of MPPOXA-PPV and PPOXA-PPV, which is an embodiment of the present invention;

4 is an electroluminescence spectrum of an electroluminescent diode using MPPOXA-PPV and PPOXA-PPV, which is an embodiment of the present invention;

5 is a graph showing voltage-current, voltage-electroluminescent intensity characteristic curve, and current-electroluminescent quantum efficiency of an electroluminescent diode using MPPOXA-PPV, which is an embodiment of the present invention;

6 is a graph showing voltage-current, voltage-electroluminescent intensity characteristic curve, and current-electroluminescence quantum efficiency of an electroluminescent diode using PPOXA-PPV, which is an embodiment of the present invention;

7 is an electroluminescence spectrum of an electroluminescent diode using MEH-PPV; And

8 is a graph showing voltage-current, voltage-electroluminescent intensity characteristic curve, and current-electroluminescent quantum efficiency of an electroluminescent diode using MEH-PPV.

According to one aspect of the present invention, the present invention provides a poly ( p -phenylenevinylene) -based organic light emitting polymer having a monomer represented by the following formula (1) as a repeating unit:

In the above formula, R ₁ , R ₂ and R ₃ are each independently an aliphatic linear alkoxy group, an aliphatic branched alkoxy group, or hydrogen, R ₄ is an aliphatic alkyl group having 2 to 14 carbon atoms, R ₅ is hydrogen or an aryl group to be.

The polymer of the present invention introduces an aromatic 1,3,4-oxadiazole group into the side chain to prevent the flow of holes, and in particular, has a structure in which an alkoxy group is inserted between the main chain and the 1,3,4-oxadiazole group. Therefore, the effect achieved by the alkoxy group and the effect achieved by the 1,3,4-oxadiazole group are suitably made in one polymer molecule.

According to a preferred embodiment of the present invention, in Formula 1, R ₁ , R ₂ and R ₃ are each independently an aliphatic linear alkoxy group, O (CH ₂ ) _x CH ₃ , and in the case of an aliphatic branched alkoxy group, OCH ₂ (CH ₂ ) _a CH (CH ₂ ) _b CH ₃ CH (CH ₃ ) ₂ , wherein x is an integer of 0 to 18, a is an integer of 0 to 4, and b is an integer of 0 to 10.

According to another preferred embodiment of the invention, the two phenyl groups bonded to the 1,3,4-oxadiazole group in the formula (1) is 1,2-, 1,3- or 1,4- relative to the alkoxy group and R ₅ It is bound to a location.

When the carbon number of R ₄ in Formula 1 is less than 2, there is a problem that the manufacturing process is difficult, and when the carbon number exceeds 14, there is a problem that it is difficult to purchase commercially. It is preferable that R <_4> is a C2-C14 aliphatic alkyl group, More preferably, it is C2-C12, Most preferably, it is C4-C10. As used herein, the term "alkyl" refers to a straight or branched or cyclic hydrocarbon compound.

As used herein, the term "aryl" refers to an aromatic hydrocarbon compound, such as phenyl, naphthyl, biphenyl, anthracenyl and the like. One or more of the carbons of the aryl group may be substituted, wherein the substituents include alkyl, aryl, heterocycle, halogen, nitro, cyano, hydroxyl, alkoxy, thio, alkyl, amino, carboxyl, and the like, It is not limited to this.

Examples of the poly ( p -phenylenevinylene) -based organic light emitting polymer of the present invention are poly {2-methoxy-5- {6 '-[2''-4'''-oxyphenyl) -5 ''- Phenyl-1 '', 3 '', 4 ''-oxadiazole] -hexyloxy} -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylene Vinylene, poly {2- [10 '-(2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole) -de Siloxy] -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene, poly {2-methoxy-5- {6 '-[2'' -4 '''-oxyphenyl]-5''-biphenyl-1'',3'',4''-oxadiazole} -hexyloxy} -1,4-phenylenevinylene-alt- 2,5-didodecyloxy-1,4-phenylenevinylene, poly {2- [10 '-(2''-(4'''-oxyphenyl) -5 ''-biphenyl-1 '',3'',4''-oxadiazole) -decyloxy] -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene Including but not limited to.

Poly {2-methoxy-5- {6 '-[2' '-4' ''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-in the above exemplary polymers Oxadiazole] -hexyloxy} -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene (abbreviated as "MPPOXA-PPV") and poly {2- [10 '-(2' '-(4' ''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole) -decyloxy]- 1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene (abbreviated as "PPOXA-PPV") is as follows:

The poly ( p -phenylenevinylene) -based organic light emitting polymer of the present invention preferably has a weight molecular weight of 8,000 to 20,000, more preferably 10,000 to 13,000, and n is preferably an integer of 10 to 15.

Since the polymer of the present invention has a structure in which 1,3,4-oxadiazole is connected to a poly ( p -phenylenevinylene) main chain through a long alkoxy group, the polymer has an effect of blocking the flow of holes. It is possible to overcome the phenomenon of shortening the lifetime of the diode by preventing the rearrangement (crystallization, etc.) of the molecular structure caused by incorporation as well as the occurrence of space charge in which the holes of the multilayer structure are concentrated toward the anode. Since the alkoxy group is bonded, the solubility in the organic solvent normally used is very excellent, and the film formation ability without defect is exceptional.

According to another embodiment of the present invention, the present invention (a) as a light emitting layer poly ( p -phenylenevinylene) organic light emitting polymer of the formula (1); (b) a metallic cathode formed on one side of the light emitting layer; And (c) an anode formed on the other side of the light emitting layer.

In the above formula, R ₁ , R ₂ and R ₃ are each independently an aliphatic linear alkoxy group, an aliphatic branched alkoxy group, or hydrogen, R ₄ is an aliphatic alkyl group having 2 to 14 carbon atoms, R ₅ is hydrogen or an aryl group to be.

Detailed description of Chemical Formula 1 is the same as that of the poly ( p -phenylenevinylene) -based organic light emitting polymer of the present invention, and thus description thereof is omitted.

In the diode of the present invention, the metallic cathode may be formed of Al, In, Al: Li alloy, Mg / Ag, Mg: Ag alloy, Ca / Ag, or Ca / Al. In addition, the anode of the diode of the present invention may be formed by vacuum deposition of indium tin oxide on an organic plastic substrate or glass.

The electroluminescent diode of the present invention has a low turn-on voltage, that is, a low operating voltage, yellow to orange color, and quantum efficiency is higher than that of a typical poly ( p -phenylenevinylene) polymer containing alkoxy. It is increased.

According to another aspect of the present invention, the present invention provides a method for preparing the poly ( p -phenylenevinylene) -based organic light emitting polymer of the formula (1).

The production method of the present invention is prepared by polymerizing aromatic bisaldehyde and aromatic bistriphenylphosphine salt by the Wittig condensation polymerization method.

At this time, a non-limiting example of the aromatic bisaldehyde used is 2,5-bis-dodecyloxy-benzene-1,4-dicarbaaldehyde (2,5-Bis-dodecyloxy-benzene- produced by the following scheme 1). 1,4-dicarbaldehyde) (Chen, Z. et al., Macromolecules , 32 : 4351 (1999)).

Also. Aromatic triphenyl pinyeom also not particularly limited, hydroxy, para-xylene (p -xylene hydroxy) or hydroxy, para-methoxy benzene (p -methoxy hydroxy benzene), and the starting materials, sequentially through the successive reaction To prepare an aromatic triphenylphosphine salt compound containing an aromatic 1,3,4-oxadiazole, and reacted with triphenylphosphine to form triphenyl containing an aromatic 1,3,4-oxadiazole as a final compound. It is preferable to prepare a phosphine salt, and the triphenylphosphine salt thus prepared is characterized in that an alkoxy group is present between the aromatic 1,3,4-oxadiazole and the aromatic triphenylphosphine salt. The aromatic triphenylphosphine salt compound thus prepared is not particularly limited, but 2-methoxy-5- {6 '-[2''-4'''-oxyphenyl) -5 ''-phenyl-1 '' , 3 '', 4 ''-oxadiazole] -hexyloxy} -p -xylene-bis-triphenylphosphonium chloride (2-Methoxy-5- {6 '-[2''-(4'''-oxyphenyl)-5''-phenyl-1'',3'',4''-oxadiazole] -hexyloxy} -p -xylene-bis- (triphenylphosphonium chloride) or 2- {4- [10- (2 , 5-Xylene-bis- (triphenylphosphonium bromide) -phenoxy) -decyloxy] -phenyl} -5-phenyl- [1,3,4] oxadiazole (2- {4- [10 It is preferable to use-(2,5-xylene-Bis- (triphenyphosphonium bromide) -phenoxy) -decyloxy] -phenyl} -5-phenyl- [1,3,4] oxadiazole). And 3.

In addition, the organic light emitting polymer produced using the above production method is not particularly limited, but poly {2-methoxy-5- {6 '-[2''-4'''-oxyphenyl) -5 '' -Phenyl-1 '', 3 '', 4 ''-oxadiazole] -hexyloxy} -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenyl Lenvinylene (poly [{2-Methoxy-5- {6 '-[2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole ] -hexyloxy}]-1,4-phenylenevinylene- alt -2,5-didodecyloxy-1,4-phenylenevinylene}, MPPOXA-PPV) or poly {2- [10 '-(2''-(4''' -Oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole) -decyloxy] -1,4-phenylenevinylene-alt-2,5-didode Siloxy-1,4-phenylenevinylene (poly {2- [10 '-(2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole) -decyloxy] -1,4-phenylenevinylene- alt -2,5-didodecyloxy-1,4-phenylenevinylene}, PPOXA-PPV), and an embodiment of the preparation method thereof is shown in Scheme 4 below. have.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it is to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. Will be self-evident.

Example 1 Preparation of Bisaldehyde (Monomer) Derivatives

Example 1-1 Preparation of 1,4-bis-dodecyloxy-benzene (1,4-Bis-dodecyloxy-benzene)

Dissolve 16.82 g (0.30 mol) of potassium hydroxide in 200 ml of methanol, dissolve 16.52 g (0.15 mol) of hydroquinone, then add 74.77 g (0.30 mol) of 1-bromododecane and under nitrogen atmosphere Heat reflux for 24 hours. The solid obtained by cooling to room temperature, filtered and washed with methanol and distilled water, then dried and recrystallized with methanol to give the title compound as a white solid in a yield of 78.3%: Melting point: 72-73 ° C ; MS [M ⁺ ]: m / z 447; ¹ H-NMR (CDCl ₃ , ppm): 6.83 (s, 4H), 3.92-3.90 (t, J = 6.6, 4H), 1.79-1.74 (m, 4H), 1.48-1.42 (m, 4H), 1.35 -1.28 (m, 32H), 0.91-0.89 (t, J = 6.6, 6H); ¹³ C-NMR (CDCl ₃ , ppm): 153.18, 115.34, 68.62, 31.92, 29.66, 29.64 29.60, 29.59, 29.42, 29.40, 29.35, 26.06, 22.69, 14.12; Calc. For C ₃₀ H ₅₄ O ₂ : C, 80.65; H, 12.18. Found: C, 80.68; H, 12.15.

Example 1-2 of 1,4, -bis-bromomethel-2,5, -bis-dodecyloxy-benzene (1,4, -Bis-bromomethyl-2,5-bis-dodecyloxy-benzene) Produce

To a mixture of 44.67 g (0.10 mol) and 30.00 g (1.0 mol) of the compound obtained in Example 1-1, HBr (30%) acetic acid solution was slowly added under a nitrogen atmosphere, stirred at 90 ° C. for 12 hours, and then room temperature After cooling to 100 ml of water and 250 ml of chloroform were added slowly and sequentially, an organic layer was obtained. The organic layer was then washed with water and aqueous sodium hydrogen carbonate solution, dried over anhydrous MgSO ₄ , filtered and evaporated and recrystallized with chloroform / methanol to give the title compound as a white solid in 63.3% yield. 95-96 ° C .; MS [M ⁺ ]: m / z 633; ¹ H-NMR (CDCl ₃ , ppm): 6.86 (s, 4H), 4.54 (s, 4H), 4.00-3.98 (t, J = 6.5, 4H), 1.85-1.79 (m, 4H), 1.53-1.47 (m, 4H), 1.37-1.28 (m, 32H), 0.91-0.87 (t, J = 6.9, 6H); ¹³ C-NMR (CDCl ₃ , ppm): 150.64, 127.49, 114.61, 68.98, 31.92, 29.67, 29.64, 29.59, 29.56, 29.35, 29.32, 28.75, 26.07, 22.69, 14.12; Calc. For C ₃₂ H ₅₆ Br ₂ O ₂ : C, 60.76; H, 8.92. Found: C, 60.78; H, 8.91.

Example 1-3 Preparation of Acetic Acid 4-acetoxymethyl-2,5-bis-dodecyloxy-benzyl ester

27.20 g (0.043 mol) of compound obtained in Example 1-2, 21.32 g (0.260 mol) of sodium acetate and 13.26 g (0.130 mol) of acetic anhydride were dissolved in 250 mL of acetic acid and heated to reflux for 24 hours under nitrogen atmosphere. I was. Then, cooled to room temperature, 200 ml of chloroform is added, the organic layer is separated, washed with water, aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous MgSO ₄ , filtered and evaporated, and then recrystallized with chloroform / methanol To afford the title compound as a white solid in 98.5% yield: Melting point: 83-84 ° C .; MS [M ⁺ ]: m / z 591; ¹ H-NMR (CDCl ₃ , ppm): 6.88 (s, 2H), 5.14 (s, 4H), 3.96-3.93 (t, J = 6.5, 4H), 2.10 (s, 6H), 1.79-1.74 (m , 4H), 1.49-1.41 (m, 4H), 1.31-1.27 (m, 32H), 0.90-0.87 (t, J = 6.8, 6H); ¹³ C-NMR (CDCl ₃ , ppm): 150.77, 125.07, 113.77, 69.01, 61.67, 31.89, 29.65, 29.61, 29.59, 29.37, 29.33, 26.04, 22.67, 21.06, 14.11; Calc. For C ₃₆ H ₆₂ 0 ₆ : C, 73.18; H, 10.58. Found: C, 73.13; H, 10.66.

Example 1-4: Obtaining (2,5-Bis-dodecyloxy-4-hydroxymethyl-phenyl) -methanol ((2,5-Bis-dodecyloxy-4-hydroxymethyl-phenyl) -methanol)

9.30 g (0.23 mol) sodium hydroxide was dissolved in 250 ml of methanol, 23.04 g (0.039 mol) of the compound obtained in Example 1-3 were added, and then heated to reflux for 12 hours under a nitrogen atmosphere. Then cooled to room temperature, the precipitate was filtered off, washed with methanol and water and recrystallized with methanol to give the title compound as a white solid in 90.6% yield: Melting point: 109-110 ° C .; MS [M ⁺ ]: m / z 507; ¹ H-NMR (CDCl ₃ , ppm): 6.85 (s, 2H), 4.68-4.67 (d, J = 6.5, 4H), 4.00-3.97 (t, J = 6.5, 4H), 2.37-2.35 (t, J = 6.5, 2H), 1.81-1.76 (m, 4H), 1.49-1.40 (m, 4H), 1.35-1.27 (m, 32H), 0.90-0.87 (t, J = 6.7, 6H); ¹³ C-NMR (CDCl ₃ , ppm): 150.64, 129.04, 112.32, 68.74, 62.20, 31.92, 29.65, 29.62, 29.59, 29.57, 29.41, 29.37, 29.34, 26.15, 22.69, 14.11; Calc. For C ₃₂ H ₅₈ O ₄ : C, 75.84; H, 11.54. Found: C, 75.88; H, 11.63.

Example 1-5: Obtaining 2,5-bis-dodecyloxy-benzene-1,4-dicarbaldehyde (2,5-Bis-dodecyloxy-benzene-1,4-dicarbaldehyde)

16.72 g (0.033 mol) of the compound obtained in Examples 1-4 and 28.00 g of celite (c electroluminescent) were added to 250 ml of dichloromethane, and pyridinium chlorochromate (PCC) at 0 ° C. 28.07 g (0.13 mol) was added to the reaction, and the degree of completion was confirmed by thin layer chromatography (mobile phase: ethyl acetate / n-hexane = 3/7). If no reactant is identified, 200 ml of diethyl ether is added to the reactant to react, the reactant is identified, and the reactant is identified. The solid compound obtained by filtration to remove the dark brown precipitate and dried is subjected to column chromatography. (Mobile phase: ethyl acetate / n-hexane = 3/7) Purification gave the title compound as a greenish yellow solid in a yield of 75.8%: Melting point: 90-91 ° C .; MS [M ⁺ ]: m / z 503; ¹ H-NMR (CDCl ₃ , ppm): 10.5 (s, 2H), 7.43 (s, 2H), 4.09-4.07 (t, J = 6.3, 4H), 1.86-1.80 (m, 4H), 1.50-1.44 (m, 4H), 1.35-1.26 (m, 32H), 0.89-0.86 (t, J = 6.8, 6H); ¹³ C-NMR (CDCl ₃ , ppm): 189.49, 155.19, 129.21, 115.53, 69.18, 31.89, 29.62, 29.60, 29.55, 29.52, 29.32, 29.29, 29.02, 25.98, 22.66, 14.11; Calc. For C32H54O4: C, 76.45; H, 10.83. Found: C, 76.37; H, 11.01

Example 2: Luminescent Polymer Poly {2-methoxy-5- {6 '-[2' '-4' ''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 '' Preparation of -oxadiazole] -hexyloxy} -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene

Example 2-1 Preparation of 1- (6-Bromo-hexyloxy) -4-methoxy-benzene (1- (6-Bromo-hexyloxy) -4-methoxy-benzene)

12.41 g (0.10 mol) of 4-hydroxy methoxy phenol, 13.8 g (0.10 mol) of potassium carbonate and 146.38 g (0.60 mol) of 1,6-dibromohexane are dissolved in 100 ml of acetone, and It was heated to reflux for a time. Then, the mixture was cooled to room temperature, filtered to remove solids, washed with 50 ml of acetone and 100 ml of chloroform, and the solvent was removed under reduced pressure. Then, 100 ml chloroform was added to the remaining residue, washed with aqueous sodium hydroxide solution and aqueous sodium chloride solution, dried over anhydrous MgSO ₄ , filtered and evaporated under reduced pressure, and the remaining filtrate was distilled under reduced pressure in vacuo to give 1,6-di. Brohexane was removed to give a colorless semisolid title compound in 91.9% yield: Melting point: 161-163 ° C./2.5 mmHg); MS [M ⁺ ]: 287; ¹ H-NMR (CDCl ₃ , ppm): 6.85 (s, 4H), 3.93-3.91 (t, J = 6.4, 2H), 3.78 (s, 3H), 3.45-3.42 (t, J = 6.8, 2H) , 1.92-1.88 (m, 2H), 1.80-1.77 (m, 2H), 1.52-1.51 (m, 4H); ¹³ C-NMR (CDCl ₃ , ppm): 153.64, 153.12, 115.32, 114.53, 68.26, 55.62, 33.72, 32.62, 29.12, 27.85, 25.22; Calc. For C ₁₃ H ₁₉ BrO ₂ : C, 54.37; H, 6.67. Found: C, 63.33; H, 8.69.

Example 2-2: 4- [6- (4-Methoxy-phenoxy) -hexyloxy] -benzoic acid methyl ester (4- [6- (4-Methoxy-phenoxy) -hexyloxy] -benzoic acid methyl ester Manufacturing

25,84 g (0.090 mol) of the compound obtained in Example 2-1, 13.8 g (0.10 mol) of potassium carbonate and 13.69 g (0.090 mol) of 4-hydroxy methyl benzoic acid ester are dissolved in 100 ml of acetone, and the nitrogen atmosphere Under reflux for 24 h. Then, the mixture was cooled to room temperature, filtered to remove solids, washed with 50 ml of acetone and 100 ml of chloroform, and distilled under reduced pressure to remove the solvent. The solid obtained was then dissolved in 100 mL chloroform, washed with an aqueous sodium hydroxide solution and an aqueous sodium chloride solution, and then dried over anhydrous MgSO ₄ , filtered and evaporated to purify the solid obtained with chloroform / methanol to give the title of a white solid. The compound was obtained in a yield of 92.5%: MS [M ⁺ ]: 358; ¹ H-NMR (CDCl ₃ , ppm): 8.00-7.99 (d, J = 8.9, 2H), 6.92-6.90 (d, J = 8.9, 2H), 6.84 (s, 4H), 4.03-4.01 (t, J = 6.5, 2H), 3.94-3.92 (t, J = 6.4, 2H), 3.89 (s, 3H), 3.77 (s, 3H), 1.86-1.79 (m, 4H), 1.56-1.55 (m, 4H ); ¹³ C-NMR (CDCl ₃ , ppm): 166.79, 162.83, 153.66, 153.16, 131.49, 122.30, 115.34, 114.55, 113.98, 68.33, 67.93, 55.63, 51.72, 29.24, 29.14, 25.79, 25.75; Calc. For C ₂₁ H ₂₆ O ₅ : C, 70.37; H, 7.31. Found: C, 75.60; H, 8.86.

Example 2-3: 4- [6- (4-Methoxy-phenoxy) -hexyloxy] -benzoic acid hydrazide (4- [6- (4-Methoxy-phenoxy) -hexyloxy] -benzoic acid hydrazide) Manufacture

28.67 g (0.080 mol) of the compound obtained in Example 2-2 and an excess of hydrated hydrazine were dissolved in 100 mL methanol and heated to reflux for 24 hours under a nitrogen atmosphere. The solid compound obtained by cooling to room temperature and filtered was then washed with 1 L of distilled water at 50 ° C. and then dried in vacuo for one day to give the title compound as a white solid in a yield of 95.6%: MS [M ⁺ ]: 358; ¹ H-NMR (CDCl ₃ , ppm): 7.71-7.69 (d, J = 8.9, 2H), 7.22 (br, 1H), 6.93-6.92 (d, J = 8.9, 2H), 6.83 (s, 4H) , 4.08 (br, 2H), 4.03-4.00 (t, J = 6.5, 2H), 3.94-3.92 (t, J = 6.5, 2H), 3.78 (s, 3H), 1.85-1.79 (m, 4H), 1.56-1.53 (m, 4 H); ¹³ C-NMR (CDCl ₃ , ppm): 168.37, 162.07, 153.74, 153.23, 128.58, 124.68, 115.44, 114.65, 114.45, 68.44, 68.04, 55.75, 29.30, 29.06, 25.85, 25.81; Calc. For C ₂₀ H ₂₆ N ₂ O ₄ : C, 67.02; H, 7.31; N, 7.82. Found: C, 72.72; H, 8.85; N, 6.81.

Example 2-4: Benzoic acid N '-{4- [6- (4-methoxy-phenoxy) -hexyloxy] -benzoyl] -hydrazide (Benzoic acid N'-{4- [6- (4 -methoxy-phenoxy) -hexyloxy] -benzoyl} -hydrazide)

A solution of 10.54 g (0.075 mol) of benzoic acid chloride dissolved in 20 ml of dimethylacetamide (DMAc) was added to 40 ml of DMAc to which 26.90 g (0.075 mol) of the compound obtained in Example 2-3 and triethylamine were added. The mixture was slowly added dropwise under a nitrogen atmosphere, stirred for 4 hours, added to methanol to form a precipitate, and the solid obtained by filtration was washed with methanol and water and purified with methanol to give the title compound as a white solid, in a yield of 89.7%. Obtained as: ¹ H-NMR (CDCl ₃ , ppm): 9.30-9.29 (d, J = 5.9, 1H), 9.20-9.18 (d, J = 5.7, 1H), 7.88-7.87 (d, J = 7.4) , 2H), 7.84-7.82 (d, J = 8.7, 2H), 7.58-7.55 (t, J = 7.4, 1H), 7.49-7.46 (t, J = 7.8, 2H), 6.95-6.93 (d, J = 8.8, 2H), 6.84 (s, 4H), 4.04-4.02 (t, J = 6.4, 2H), 3.95-3.92 (t, J = 6.4, 2H), 3.77 (s, 3H), 1.86-1.80 ( m, 4H), 1.57-1.54 (m, 4H); ¹³ C-NMR (CDCl ₃ , ppm): 163.80, 162.57, 153.74, 153.23, 150.82, 132.41, 131.44, 129.08, 128.81, 127.54, 127.17, 123.55, 115.44, 114.65, 68.44, 68.11, 55.75, 29.31, 29.05, 29.05 , 25.80; Calc. For C ₂₇ H ₃₀ N ₂ O ₅ : C, 70.11; H, 6. 54; N, 6.06. Found: C, 74.35; H, 7.83; N, 5.47.

Example 2-5: 2-methoxy-5- {6 '[2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxa Diazole] -hexyloxy} -p -xylene (2-Methoxy-5- {6 '-[2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '' , 4 ''-oxadiazole] -hexyloxy} -p -xylene)

30.99 g (0.0670 mol) of the compound obtained in Example 2-4 was dissolved in 150 ml of POCl ₃ , heated to reflux for 6 hours to remove excess POCl _3, and then slowly added the reactant to ice water to form a precipitate. And filtered to give a precipitate, which was then washed with 1 L of distilled water. Subsequently, washed with 1 N aqueous sodium hydroxide solution and aqueous sodium chloride solution dissolved in 200 ml of chloroform to remove any remaining acid, and the organic layer was dried with anhydrous MgSO ₄ , filtered, and evaporated to obtain a solid obtained by methanol. The title compound was obtained in a yield of 88.3%: MS [M ⁺ ]: m / z 444; ¹ H-NMR (CDCl ₃ , ppm): 8.14-8.12 (m, 2H), 8.07-8.05 (d, J = 8.7, 2H), 7.55-7.52 (m, 3H), 7.03-7.01 (d, J = 8.8, 2H), 6.84 (s, 4H), 4.06-4.03 (t, J = 6.5, 2H), 3.95-3.92 (t, J = 6.4, 2H), 3.77 (s, 3H), 1.87-1.80 (m , 4H), 1.58-1.55 (m, 4H); ¹³ C-NMR (CDCl ₃ , ppm): 164.53, 164.04, 161.86, 153.69, 153.18, 131.43, 128.97, 128.62, 126.75, 124.09, 116.19, 115.38, 114.93, 114.59, 68.37, 68.05, 55.67, 29.26, 29.02, 25.02 , 25.78; Calc. For C ₂₇ H ₂₈ N ₂ O ₄ : C, 72.95; H, 6. 35; N, 6.30. Found: C, 77.08; H, 7.71; N, 5.62.

Example 2-6: 1,4-bis-chloromethyl (-2-methoxy) -5- {6 '-[2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole] -hexyloxy} -benzene (1,4-Bis-chloromethyl- (2-methoxy) -5- {6 '-[2''-(4'''-oxyphenyl)-5''-phenyl-1'',3'',4''-oxadiazole] -hexyloxy} -benzene)

100 ml of 37% hydrochloric acid was slowly added dropwise to 50 ml of 1,4-dioxane in which 5.29 g (11.90 mmol) of the compound obtained in Example 2-5 and 1.903 g (47.58 mmol) of paraformaldehyde were dissolved. 200 ml of acetic anhydride was slowly added dropwise, and stirred at 65 ° C. for 10 hours, cooled to room temperature, and 200 ml of water was added to form a precipitate. Subsequently, the precipitate obtained by filtration was washed with distilled water, dissolved in 100 ml of chloroform, washed with aqueous sodium bicarbonate solution and brine, an organic layer was obtained, and then dried over anhydrous MgSO ₄ , filtered, and evaporated. Removed. The remaining solid compound was then purified with chloroform / methanol to give the title compound as a white solid in a yield of 62.5%: [M-Cl] ⁺ : m / z 505. MS; ¹ H-NMR (CDCl ₃ , ppm): 8.14-8.12 (m, 2H), 8.07-8.05 (d, J = 8.9, 2H), 7.54-7.53 (m, 3H), 7.03-7.01 (d, J = 8.8, 2H), 6.93 (s, 1H), 6.92 (s, 1H), 4.64 (s, 1H), 4.63 (s, 1H), 4.07-4.05 (t, J = 6.4, 2H), 4.03-4.01 ( t, J = 6.3, 2H), 3.85 (s, 3H), 1.89-1.85 (m, 4H), 1.60-1.59 (m, 4H); ¹³ C-NMR (CDCl ₃ , ppm): 164.54, 164.04, 161.86, 151.02, 150.58, 131.45, 128.98, 128.63, 127.03, 126.82, 126.76, 124.06, 116.16, 114.93, 114.36, 113.29, 66.80, 68.01, 56.20, 41.20 , 41.24, 29.18, 29.01, 25.78, 25.69. Calc. For C ₂₉ H ₃₀ Cl ₂ N ₂ O ₄ : C, 64.33; H, 5.58; N, 5.17. Found: C, 58.53; H, 5.56; N, 4.19.

Examples 2-7: 2-methoxy-5- {6 '-[2''-4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxa Diazole] -hexyloxy} -p -xylene-bis-triphenylphosphonium chloride (2-Methoxy-5- {6 '-[2''-(4'''-oxyphenyl) -5 ''-phenyl -1 '', 3 '', 4 ''-oxadiazole] -hexyloxy} -p -xylene-bis- (triphenylphosphonium chloride)

10 ml of dimethylformamide in which 1.12 g (2.08 mmol) of the compound obtained in Example 2-6 and 1.20 g (4.58 mmol) of triphenylphosphine were dissolved were heated to reflux under a nitrogen atmosphere for 24 hours, and then cooled to room temperature. Then, slowly added dropwise to diethyl ether to form a precipitate, which was filtered to obtain a precipitate. The precipitate obtained was then washed with 500 ml of diethyl ether and purified with methanol and diethyl ether mixed solvent to give the title compound in 85.4% yield: ¹ H-NMR (CDCl ₃ , ppm): 8.11 -8.09 (m, 2H), 8.06-8.04 (d, J = 8.9, 2H), 7.71-7.61 (m, 30H), 7.54-7.49 (m, 3H), 7.04-7.02 (d, J = 9.0, 2H ), 6.90 (s, 1H), 6.80 (s, 1H), 5.35-5.30 (m, 4H), 4.04-4.02 (t, J = 6.3, 2H), 3.12-3.10 (t, J = 5.5, 2H) 2.88 (s, 3H), 1.78-1.75 (m, 4H), 1.37-1.35 (m, 4H); ¹³ C-NMR (CDCl ₃ , ppm): 164.48, 164.07, 161.81, 150.83, 150.54, 134.75, 134.74, 134.66, 134.64, 134.31, 134.29, 134.24, 134.22, 131.47, 129.99, 129.93, 129.90, 129.68, 128.84. , 126.75, 124.00, 134.76, 134.74, 134.66, 134.64, 134.31, 134.29, 134.24, 134.22, 118.47, 118.41, 117.78, 117.72, 16.55, 116.47, 117.72, 16.55, 116.47, 116.45, 116.26, 115,45. , 28.60, 25.72, 25.55; Calc. For C ₆₅ H ₆₀ Cl ₂ N ₂ O ₄ P ₂ : C, 73.23; H, 5.67; N, 2.63. Found: C, 69.21; H, 5.69; N, 2.31

Example 2-8: poly {2-methoxy-5- {6 '-[2''-4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 '' -Oxadiazole] -hexyloxy} -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene ([{2-Methoxy-5- {6 '-[2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole] -hexyloxy}]-1,4-phenylenevinylene- alt -2 , 5-didodecyloxy-1,4-phenylenevinylene}) (MPPOXA-PPV)

5 ml of anhydrous ethanol was slowly added to 0.12 g (5.0 mmol) of sodium metal at 0 ° C. under a nitrogen atmosphere and stirred at room temperature for 30 minutes to prepare an ethoxide sodium solution, and the title compound obtained in Example 1-5. And the title compound obtained in Example 2-7 were dissolved in 15 ml of anhydrous chloroform at a concentration of 1 mmol, respectively, to prepare a monomer solution.

Each prepared monomer solution was mixed, the ethoxy sodium solution was added dropwise, stirred at room temperature for 2 days, poured into excess methanol in the reaction, a precipitate was formed, and then filtered to obtain a precipitate. The precipitate obtained was washed with water and methanol, dissolved again in a small amount of chloroform, reprecipitated in excess methanol, purified, and then purified using a Soxhlet extractor to remove low molecular weight products. Purification over days afforded the title compound in a yield of 45%: ¹ H-NMR (CDCl ₃ , ppm): 8.19-8.02 (m, 9H, H of aromatic 1,3,4-oxadiazole), 7.68 -7.32 (m, 2H, aromatic H of the main chain), 7.08-6.82 (m, 6H, vinyl H), 4.18-4.08 (m, 11H), 1.98-1.05 (m, 48H), 0.98-0.90 (m, 6H ); Calc. For C ₆₁ H ₈₂ N ₂ O ₆ : C, 78.00; H, 8. 80; N, 2.98; Found: C, 77.33; H, 8.71; N, 2.20.

Example 3. Luminescent Polymer Poly {2- [10 '-(2' '-(4' ''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole Preparation of) -decyloxy] -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene

Example 3-1 Preparation of 2- (10-Bromo-decyloxy) -1,4-dimethylbenzene (2- (10-Boromo-decyloxy) -1,4-dimethyl-benzene)

120.03 g (0.40 mol) of 1,10-dibromodecane, 13.82 g (0.10 mol) of anhydrous potassium carbonate and 12.22 g (0.10 mol) of 2,5-dimethylphenol are dissolved in 100 ml of anhydrous acetone and under nitrogen atmosphere The mixture was heated to reflux for 24 hours, cooled to room temperature, filtered to remove precipitates, washed with 100 ml of acetone, and dried under reduced pressure. The remaining residue was then dissolved in 150 ml of chloroform and washed with 200 ml of 1 N aqueous sodium hydroxide solution and 300 ml of saturated aqueous sodium chloride solution. Then, the organic layer was separated, dried over anhydrous MgSO ₄ , filtered and evaporated under reduced pressure, and the remaining residue was distilled under reduced pressure in vacuo to completely remove 1,10-dibromodecane, thereby obtaining the title compound as a colorless liquid 75.4. Obtained in% yield: Break point: 160-162 ° C./0.5 mmHg); [M ⁺ ]: m / z 342; ¹ H-NMR (CDCl ₃ , ppm): 7.02-7.00 (d, J = 7.4, 1H), 6.67-6.65 (d, J = 7.5, 1H), 6.64 (s, 1H), 3.95-3.93 (t, J = 6.4, 2H), 3.43-3.40 (t, J = 6.8, 2H), 2.32 (s, 3H), 2.18 (s, 3H), 1.89-1.83 (m, 2H), 1.82-1.76 (m, 2H ), 1.51-1.42 (m, 4H), 1.37-1.32 (m, 12H); ¹³ C-NMR (CDCl ₃ , ppm): 157.09, 136.40, 130.23, 123.60, 120.53, 111.98, 67.81, 34.01, 32.81, 29.44, 29.37, 29.34, 29.30, 28.73, 28.15, 26.11, 21.39, 15.77; Calc. For C ₁₈ H ₂₉ BrO: C, 63.34; H, 8.56. Found: C, 63.33; H, 8.69.

Example 3-2: 4- [10- (2,5-Dimethyl-phenoxy) -decyloxy] -benzoic acid methyl ester (4- [10- (2,5-Dimethyl-phenoxy) -decyloxy] -benzoic acid methyl ester)

12.63 g (0.037 mol) of the compound obtained in Example 3-1, 5.63 g (0.037 mol) of 4-hydroxy methyl benzoester and 5.11 g (0.037 mol) of potassium carbonate were dissolved in 150 ml of anhydrous acetone and nitrogen atmosphere. The mixture was heated to reflux for 24 hours, cooled to room temperature, filtered to remove the precipitate, washed with 100 ml of acetone, and distilled under reduced pressure to remove the solvent. The residue was then dissolved in 150 ml chloroform, washed with 200 ml 1 N aqueous sodium hydroxide solution and 300 ml saturated aqueous sodium chloride solution, and then the organic layer was separated, dried over anhydrous MgSO ₄ , filtered and distilled under reduced pressure to remove the solvent. . The remaining residue was then purified by silica gel column chromatography (mobile phase: diethyl ether / n-hexane = 2/8) to give the title compound as a white solid in a yield of 93.7%. Melting point: 47 -48 ° C; [M ⁺ ]: m / z 412; ¹ H-NMR (CDCl ₃ , ppm): 7.99-7.97 (d, J = 6.8, 2H), 7.01-7.00 (d, J = 7.3, 1H), 6.91-6.89 (d, J = 6.8, 2H), 6.66-6.65 (d, J = 7.3, 1H), 6.63 (s, 1H), 4.02-3.99 (t, J = 6.3, 2H), 3.95-3.92 (t, J = 6.3, 2H), 3.88 (s, 3H), 2.31 (s, 3H), 2.18 (s, 3H), 1.81-1.77 (m, 4H), 1.49-1.45 (m, 4H), 1.38-1.34 (m, 8H); ¹³ C-NMR (CDCl ₃ , ppm): 166.90, 162.95, 157.11, 136.41, 131.54, 130.24, 123.61, 122.32, 120.54, 114.05, 111.99, 68.18, 67.82, 51.79, 29.49, 29.46 29.39, 29.33, 29.10, 26.10 25.96, 21.39, 15.77; Calc. For C ₂₆ H ₃₆ O ₄ : C, 75.69; H, 8.80. Found: C, 75.60; H, 8.86.

Example 3-3 4- [10- (2,5-Dimethyl-phenoxy) -decyloxy] -benzoic acid hydrazide (4- [10- (2,5-Dimethyl-phenoxy) -decyloxy] -benzoic acid hydrazide).

11.14 g (0.027 mol) of the compound obtained in Example 3-2 and an excess of hydrated hydrazine were dissolved in 100 ml methanol, heated to reflux for 24 hours under a nitrogen atmosphere, cooled to room temperature, and filtered to obtain a precipitate. Obtained. Then washed with 1 L of distilled water at 50 ° C. and dried in vacuo for one day to give the title compound as a white solid in a yield of 94.2%: Melting point: 92-93 ° C. [M ⁺ ]: m / z 413; ¹ H-NMR (CDCl ₃ , ppm): 7.70-7.68 (d, J = 6.8, 2H), 7.28 (b, 1H), 7.01-6.99 (d, J = 7.4, 1H), 6.93-6.91 (d, J = 6.8, 2H), 6.66-6.65 (d, J = 7.4, 1H), 6.63 (s, 1H), 4.07 (b, 2H), 4.00-3.98 (t, J = 6.5, 2H), 3.95-3.92 (t, J = 6.4, 2H), 2.31 (s, 3H), 2.17 (s, 3H), 1.81-1.76 (m, 4H), 1.49-1.44 (m, 4H), 1.38-1.34 (m, 8H) ; ¹³ C-NMR (CDCl ₃ , ppm): 168.38, 162.11, 157.10, 136.42, 130.24, 128.57, 124.58, 123.60, 120.54, 114.43, 111.99, 68.19, 67.82, 29.48, 29.45, 29.38, 29.32, 29.08, 26.12, 25.12 , 21.39, 15.77; Calc. For C ₂₅ H ₃₆ N ₂ O ₃ : C, 72.78; H, 8. 80; N, 6.79. Found: C, 72.72; H, 8.85; N, 6.81.

Example 3-4: Benzoic acid N- {4- [10- (2,5-dimethyl-phenoxy) -decyloxy] -benzoyl} -hydrazide (Benzoic acid N- {4- [10- (2, 5-dimethyl-phenoxy) -decyloxy] -benzoyl} -hydrazide)

A solution of 1.83 g (0.013 mol) of benzoic acid chloride dissolved in 20 ml of methane dichloride was dissolved in 5.36 g (0.013 mol) of the compound obtained in Example 3-3 and 1.32 g (0.013 mol) of triethylamine. To the solution dissolved in methane was slowly added dropwise under nitrogen atmosphere and stirred for 4 hours. Then, washed with distilled shoe and aqueous sodium chloride solution, the organic layer was separated, dried over anhydrous MgSO ₄ , filtered and evaporated, and then purified with methanol to give the title compound as a white solid in a yield of 82.5%. 138-139 ° C. [M + H] ⁺ : m / z 517; ¹ H-NMR (CDCl ₃ , ppm): 9.24-9.22 (d, J = 6.8, 1H), 9.13-9.12 (d, J = 6.3, 1H), 7.88-7.86 (d, J = 7.3, 2H), 7.83-7.82 (d, J = 8.8, 2H), 7.58-7.55 (t, J = 7.3, 1H), 7.50-7.47 (t, J = 7.8, 2H), 7.01-6.99 (d, J = 7.8, 1H ), 6.96-6.94 (d, J = 8.8, 1H), 6.66-6.64 (d, J = 7.3, 1H), 6.64 (s, 1H), 4.03-4.00 (t, J = 6.3, 2H), 3.95- 3.93 (t, J = 6.3, 2H), 2.31 (s, 3H), 2.18 (s, 3H), 1.83-1.76 (m, 4H), 1.48-1.44 (m, 4H), 1.38-1.35 (m, 8H ); ¹³ C-NMR (CDCl ₃ , ppm): 163.91, 163.76, 162.61, 157.12, 136.43, 132.39, 131.45, 130.25, 129.10, 128.79, 127.19, 123.63, 123.20, 120.549, 114.53, 112.01, 68.27, 29.84, 29.5 , 29.39, 29.35, 29.34, 29.09, 26.14, 25.97, 21.40, 15.78; Calc. For C ₃₂ H ₄₀ N ₂ O ₄ : C, 74.39; H, 7.80; N, 5.42. Found: C, 74.35; H, 7.83; N, 5.47.

Examples 3-5: 2- {4- [10- (2,5-Dimethyl-phenoxy) -decyloxy] -phenyl} -5-phenyl- [1,3,4] oxadiazole (2- Preparation of {4- [10- (2,5-Dimethyl-phenoxy) -decyloxy] -phenyl} -5-phenyl- [1,3,4] oxadiazole)

3.60 g (6.97 mmol) of the compound obtained in Example 3-4 were dissolved in 50 mL of POCl ₃ , heated to reflux for 6 hours to remove excess POCl _3, and then slowly added dropwise to the reaction mixture with ice water to form a precipitate. And filtered to give a precipitate. The precipitate was washed with 500 ml of distilled water, dissolved in 100 ml chloroform and washed with 1N aqueous sodium hydroxide solution and aqueous sodium chloride solution to remove any remaining acid. The organic layer was then separated, dried over anhydrous MgSO ₄ , filtered and evaporated to remove the solvent, and then the remaining solid compound was purified with methanol to give the title compound as a white solid in 94.0% yield. Melting point: 95- 96 ° C. [M ⁺ ]: m / z 498; ¹ H-NMRCDCl ₃ , ppm): 8.14-8.13 (m, 2H), 8.08-8.06 (d, J = 8.8, 2H), 7.54-7.52 (m, 3H), 7.03-7.00 (m, 3H), 6.66 -6.65 (d, J = 7.8, 1H), 6.64 (s, 1H), 4.05-4.03 (t, J = 6.8, 2H), 3.95-3.93 (t, J = 6.8, 2H), 2.31 (s, 2H ), 2.18 (s, 3H), 1.85-1.78 (m, 4H), 1.48-1.44 (m, 4H), 1.38-1.35 (m, 8H); ¹³ C-NMR (CDCl ₃ , ppm): 164.60, 164.08, 161.97, 157.11, 136.41, 131.47, 130.24, 129.01, 128.66, 126.81, 124.15, 123.61, 120.55, 116.18, 114.98, 112.00, 68.26, 67.83, 29.49 46 , 29.39, 29.34, 29.12, 26.13, 25.98, 21.39, 15.77; Calc. For C ₃₂ H ₃₈ N ₂ O ₃ : C, 77.08; H, 7.68; N, 5.62. Found: C, 77.08; H, 7.71; N, 5.62.

Example 3-6: 2- {4- [10- (2,5-bis-bromomethyl-phenoxy) -decyloxy] -phenyl- [1,3,4] oxadiazole (2- { Obtaining 4- [10- (2,5-Bis-bromomethyl-phenoxy) -decyloxy] -phenyl} -5-phenyl- [1,3,4] oxadiazole)

3.00 g (6.02 mmol) of the compound obtained in Example 3-5, 200 mL of carbon tetrachloride added with 2.31 g (0.013 mol) of N-bromo succinimide and a catalytic amount of benzoyl peroxide were refluxed under a nitrogen atmosphere for 8 hours. The mixture was cooled to room temperature, washed with brine, and the organic layer was separated. The organic layer was dried over MgSO ₄ , filtered, and evaporated to remove the solvent, and the remaining solid was dissolved in chloroform, and then added dropwise to diethyl ether to form a precipitate, yielding the title compound as a white solid in a yield of 55.5%. Obtained: Melting point: 108-109 ° C .; MS [M + H] ⁺ : m / z 657; ¹ H-NMR (CDCl ₃ , ppm): 8.14-8.13 (m, 2H), 8.09-8.06 (d, J = 8.5, 2H), 7.55-7.52 (m, 3H), 7.30-7.28 (d, J = 7.7, 1H), 7.05-7.02 (d, J = 8.8, 2H), 6.94-6.91 (d, J = 7.7, 1H), 6.89 (s, 1H), 4.54 (s, 2H), 4.46 (s, 2H ), 4.07-4.03 (m, 4H), 1.90-1.79 (m, 4H), 1.54-1.46 (m, 4H), 1.42-1.37 (m, 8H); ¹³ C-NMR (CDCl ₃ , ppm): 164.61, 164.10, 161.97, 157.12, 139.77, 131.49, 131.04, 129.02, 128.68, 126.83, 126.51, 124.14, 120.96, 116.19, 114.99, 112.29, 6845, 29.27, 33.32, 33.32 , 29.33, 29.28, 29.15, 29.12, 29.06, 28.48, 26.05, 25.98; Calc. For C ₃₄ H ₃₁ N ₂ O ₃ : C, 58.55; H, 5.53; N, 4.27. Found: C, 58.53; H, 5.56; N, 4.19.

Example 3-7: 2- {4- [10- (2,5-Xylene-bis- (triphenylphosphonium bromide) -phenoxy) -decyloxy] -phenyl} -5-phenyl- [1 , 3,4] oxadiazole (2- {4- [10- (2,5-xylene-Bis- (triphenyphosphonium bromide) -phenoxy) -decyloxy] -phenyl} -5-phenyl- [1,3,4 ] oxadiazole)

10 mL of dimethylformamide in which 1.31 g (2.00 mmol) of the compound obtained in Example 3-6 and 1.15 g (4.40 mmol) of triphenylphosphine were dissolved was heated to reflux under a nitrogen atmosphere for 24 hours, and cooled to room temperature. Then, the mixture was slowly added dropwise to diethyl ether to form a precipitate, followed by filtration to obtain a precipitate. The precipitate was then washed with 500 mL of diethyl ether and purified using a mixed solvent of methanol and diethyl ether to give the title compound in a yield of 50.4%: Melting point: 193-194 ° C .; ¹ H-NMR (CDCl ₃ , ppm): 8.11-8.09 (m, 2H), 8.05-8.04 (d, J = 8.8, 2H), 7.74-7.58 (m, 30H), 7.54-7.49 (m, 3H) , 7.12-7.11 (d, J = 5.4, 1H), 7.02-7.00 (d, J = 8.8, 2H), 6.77 (s, 1H), 6.27-6.25 (d, J = 6.0, 1H), 5.32-5.26 (m, 4H), 4.05-4.03 (t, J = 6.5, 2H), 3.04-3.02 (t, J = 5.7, 2H), 1.84-1.79 (m, 2H), 1.50-1.45 (m, 2H), 1.40-1.07 (m, 12 H); ¹³ C-NMR (CDCl ₃ , ppm): 164.09, 163.60, 161.47, 134.63, 134.45, 134.43, 133.95, 133.87, 133.65, 133.57, 133.24, 133.16, 131.04, 130.03, 129.93, 129.82, 129.72, 129.66. , 128.18, 126.30, 123.57, 117.84, 117.26, 117.16, 116.58, 115.66, 114.51, 67.77, 67.49, 29.04, 29.02, 28.90, 28.82, 28.70, 28.65, 28.09, 25.53, 25.37; Calc. For C ₆₈ H ₆₆ Br ₂ N ₂ O ₃ P ₂ : C, 69.15; H, 5.63; N, 2.37. Found: C, 69.21; H, 5.69; N, 2.31

Example 3-8: Poly {2- [10 '-(2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole ) -Decyloxy] -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene ({2- [10 '-(2''-(4'''-oxyphenyl)-5''-phenyl-1'',3'',4''-oxadiazole) -decyloxy] -1,4-phenylenevinylene- alt -2,5-didodecyloxy-1,4-phenylenevinylene }) Preparation of (PPOXA-PPV)

The title compound was prepared in 45% yield using the same method as Example 2-8 except for using the compound obtained in Example 3-7 instead of the compound obtained in Example 2-7. ¹ H-NMR (CDCl ₃ , ppm): 8.19-8.02 (m, 9H, H of aromatic 1,3,4-oxadiazole), 7.68-7.32 (m, 2H, aromatic H of main chain), 7.08- 6.82 (m, 6H, vinyl H), 4.18-4.08 (m, 8H), 1.98-1.05 (m, 56H), 0.98-0.90 (m, 6H); Calc. For C ₅₇ H ₇₄ N ₂ O ₅ : C, 78.76; H, 8.58; N, 3.22; Found: C, 76.14; H, 9. 15; N, 3.14.

Example 4 Fabrication of Light Emitting Diodes and Their Characterization

Example 4-1 Fabrication of Light Emitting Diodes Using MPPOXA-PPV

Using the light emitting polymer MPPOXA-PPV prepared in Example 2-8, a light emitting diode having a monolayer structure was prepared by the following method:

First, MPPOXA-PPV, a light emitting polymer prepared in Example 2-8, was dissolved in 1,1,2,2-tetrachloroethane (1,1,2,2-tetrachloroethane, TCE) at a concentration of 25 mg / ml. In addition, fine particles and foreign matter present in the light emitting polymer solution were removed by using a membrane filter and a syringe having a pore size of 0.45 μm. Meanwhile, the glass plate coated with ITO was washed, the light-emitting polymer solution was spin-coated at 1500 rpm, dried in vacuo for 2 hours, and the aluminum electrode was vacuum-deposited thereon under a pressure of 10 ^-5 torr or lower. A light emitting diode was manufactured. The thickness of the aluminum film was maintained at 1,000 to 1,500 mW using a Sigma crystal sensor, and the area of the aluminum film was fixed at 4 mm ² using a mask. A schematic structure of the LED thus manufactured is shown in FIG. 1.

Example 4-2 Fabrication of Light Emitting Diodes Using PPOXA-PPV

A light emitting diode was manufactured in the same manner as in Example 4-1, except that the light emitting polymer PPOXA-PPV prepared in Example 3-8 was used instead of the light emitting polymer MPPOXA-PPV prepared in Example 2-8. Prepared.

Example 4-3 Optical Characteristics of Light Emitting Diodes

In order to determine the optical characteristics of the light emitting diodes manufactured in Examples 4-1 and 4-2. Each thin film was prepared by spin coating each of the luminescent polymer solutions prepared in Examples 4-1 and 4-2 onto a quartz plate, and then using an absorption spectrum analyzer (8453, Hewlett-Pakard, USA). Then, the absorbance (UV-visible) spectrum of each thin film was measured, and the luminescence (photoluminescence, PL) spectrum of each thin film was measured using a fluorescent (PTI, USA). The results are shown in FIGS. 2 and 3.

Figure 2 is a graph showing the degree of absorption according to the wavelength of each thin film, it can be seen that both MPPOXA-PPV and PPOXA-PPV shows an absorption peak at 302 nm, which is an aromatic 1,3,4-oxadiazole The absorption peak corresponds to the absorption peak of 444 nm of MPPOXA-PPV and 454 nm of PPOXA-PPV, respectively, corresponding to the π-π ^* transition of the main chain. In addition, the absorption edge wavelengths of MPPOXA-PPV and PPOXA-PPV were 595 nm and 567 nm, respectively.

FIG. 3 is a graph showing the degree of excitation of each thin film according to the wavelength. When MPPOXA-PPV was excited at 460 nm, the maximum peak of the photoluminescence (PL) spectrum appeared at 585 nm and PPOXA-PPV at 450 nm. The maximum peak of the PL spectrum when excited is 557 nm, and the PL peak of the aromatic 1,3,4-oxadiazole corresponding to the side chain when the MPPOXA-PPV and PPOXA-PPV thin films are excited at 302 nm (360 nm) It can be seen that does not appear.

2 and 3, it can be seen that all energy is transferred from the aromatic 1,3,4-oxadiazole to the main chain of the light emitting polymer. That is, the MPPOXA-PPV absorption peak is blue-shifted about 10 nm shorter wavelength compared to PPOXA-PPV, while the maximum PL peak is the spectrum where MPPOXA-PPV is red-shifted toward the 28 nm long wavelength. In the case of MPPOXA-PPV, the absorption peak is short due to steric hindrance because the length of the alkoxy group between the polymer main chain and aromatic 1,3,4-oxadiazole is shorter than that of PPOXA-PPV. In the case of MPPOXA-PPV, which has more methoxy groups than PPOXA-PPV, the maximum peak of PL is shifted toward the longer wavelength because of the electron donor (electroluminescence-donationg) effect of this methoxy group. Analyzed.

Example 4-4 Electroluminescence Spectrum of Light Emitting Diodes

The electroluminescence (electroluminescence) spectra of the light emitting diodes prepared in Examples 4-1 and 4-2 were measured using a fluorometer (PTI, U.S.A.), and the results are shown in FIG. 4.

As can be seen in Figure 4, the maximum emission peak of MPPOXA-PPV emits light in the orange region at 586 nm, the maximum emission peak of PPOXA-PPV emits light in the yellow region at 559 nm, the MPPOXA-PPV is 28 The shift to the red region by nm is analyzed for the same reason as in the PL spectrum.

Example 4-5: Voltage-Current, Voltage-Electroluminescent Intensity Characteristic Curve, and Current-Electroluminescent Quantum Efficiency of Electroluminescent Diode

The relationship between the voltage-current, voltage-electroluminescent intensity characteristic curve, and current-electroluminescence quantum efficiency of the light emitting diodes manufactured in Examples 4-1 and 4-2 was measured, and the results are shown in FIGS. 5 and 6. . In other words, Newport's Model 818UV / CM photodiode and Newport's 1830 powermeter were measured by applying a forward bias voltage to the electroluminescent device and measuring the current flowing, while correcting the intensity of light emitted from the electroluminescent device. It measured using. At this time, the distance between the electroluminescent element and the photodiode is 5 mm. Quantum efficiency was calculated by substituting the current value flowing through the measured electroluminescent device and the electroluminescent intensity measured by the calibrated photodiode into the following formula.

h = 6.626 10 ^-34 Js ^-1 (Planck's constant)

λ = maximum wavelength in the electroluminescent spectrum

Time (s): measurement time

Time (s): measurement time

5 is a graph showing voltage-current, voltage-electroluminescent intensity characteristic curve and current-electroluminescent quantum efficiency of MPPOXA-PPV, and FIG. 6 is voltage-current, voltage-electroluminescent intensity characteristic curve and current of PPOXA-PPV. -As a graph showing the electroluminescence quantum efficiency, in FIG. 5 and FIG. 6, (o) represents current with respect to voltage, and (o) represents electroluminescence intensity with respect to voltage. As can be seen in Figures 5 and 6, both electroluminescent diodes using MPPOXA-PPV and PPOXA-PPV exhibit the characteristics of a typical rectifying diode, the turn-on voltage is 4.5 V, respectively. The maximum quantum efficiency of the electroluminescent diode using MPPOXA-PPV was 0.016%, and the maximum quantum efficiency of PPOXA-PPV was 0.021%.

Therefore, when aromatic 1,3,4-oxadiazole is connected to the side chain in a distant form from the main chain, aromatic 1,3,4-oxadiazole prevents the occurrence of space charge in which holes are biased toward the cathode. At the same time, since electrons injected from the cathode can effectively meet in the light emitting layer (hole-electroluminescence ectron recombination), the light emission efficiency is increased, and the current flowing through the electroluminescent diode is small, so that the current consumption can be minimized. Heat generation also minimized the lifetime of the diode.

Comparative Example 1 Optical Characteristics of Electroluminescent Diode Using MEH-PPV

In order to demonstrate the superiority of the electroluminescent polymer of the present invention, instead of the luminescent polymer MPPOXA-PPV prepared in Example 2-8, MEH (Poly (1-methoxy-4-ethlyhexyloxy-1,5) Except for using -phenylenevinylene))-PPV, an electroluminescent diode was manufactured in the same manner as in Example 4-1, and its electroluminescence spectrum was measured. The results are shown in FIG. The relationship between the current, the voltage-electroluminescent intensity characteristic curve, and the current-electroluminescent quantum efficiency was measured and the results are shown in FIG. 8.

7 is an electroluminescence spectrum of the electroluminescent diode having a single layer structure using MEH-PPV, the maximum emission wavelength was 590 nm. 8 is a graph showing the relationship between the voltage-current, voltage-electroluminescent intensity characteristic curve, and current-electroluminescent quantum efficiency of an electroluminescent diode using MEH-PPV. In FIG. (▲) indicates the electroluminescence intensity with respect to the voltage, and the maximum luminous efficiency was 0.0002% and the on voltage was found to be 8V. Therefore, it can be seen that the electroluminescent diode using the organic light emitting polymer of the present invention is excellent in all respects.

As can be seen in the above embodiment, the electroluminescent diode of the present invention showed a turn-on voltage of 4 to 5 V, emitted from yellow to orange, and had a quantum efficiency of 0.01 to 0.02%. On the other hand, compared with the turn-on voltage and quantum efficiency of light emitting diodes prepared using alkoxy-modified poly ( p -phenylenevinylene) prepared by a conventional method as the light emitting layer, the efficiency of the diamond of the present invention is 50 to 100 times. It could be confirmed that the increase.

The present invention provides a novel poly ( p -phenylenevinylene) -based organic light emitting polymer that can effectively block the flow of holes. In addition, the present invention provides an electroluminescent diode having a very good quantum efficiency and a low operating voltage. Since the polymer of the present invention has a structure in which 1,3,4-oxadiazole is connected to a poly ( p -phenylenevinylene) main chain through a long alkoxy group, the polymer has an effect of blocking the flow of holes. It can overcome the phenomenon of shortening the lifetime of the diode by preventing the rearrangement (crystallization, etc.) of the molecular structure caused by incorporation as well as the occurrence of space charge in which the holes of the multilayer structure are concentrated toward the anode. Since the alkoxy group is bonded, the solubility in the organic solvent normally used is very excellent, and the film formation ability without defect is exceptional. In addition, the electroluminescent diode of the present invention has a low ON voltage, that is, an operating voltage, emits yellow to orange, and has significantly increased quantum efficiency than a general poly ( p -phenylenevinylene) -based polymer containing alkoxy.

Claims (8)

A poly ( p -phenylenevinylene) -based organic light emitting polymer having a monomer represented by the following Formula 1 as a repeating unit: Formula 1 In the above formula, R ₁ , R ₂ and R ₃ are each independently an aliphatic linear alkoxy group, an aliphatic branched alkoxy group, or hydrogen, R ₄ is an aliphatic alkyl group having 2 to 14 carbon atoms, and R ₅ is hydrogen or an aryl group to be. According to claim 1, wherein in Formula 1 R ₁ , R ₂ and R ₃ are each independently an aliphatic linear alkoxy group is O (CH ₂ ) _x CH ₃ , when the aliphatic branched alkoxy group is OCH ₂ (CH ₂ ) _a CH (CH ₂ ) _b CH ₃ CH (CH ₃ ) ₂ , wherein x is an integer of 0-18, a is an integer of 0-4, and b is an integer of 0-10. p -phenylenevinylene) type organic light emitting polymer. According to claim 1, wherein the two phenyl groups bonded to the 1,3,4-oxadiazole group in the formula 1 is bonded to the 1,2-, 1,3- or 1,4- position relative to the alkoxy group and R ₅ Poly ( p -phenylenevinylene) type organic light emitting polymer which is characterized by the above-mentioned. The poly ( p -phenylenevinylene) organic light emitting polymer according to claim 1, wherein R ₄ is an aliphatic alkyl group having 4 to 10 carbon atoms. The method of claim 1, wherein the poly ( p -phenylenevinylene) -based organic light emitting polymer is poly {2-methoxy-5- {6 '-[2''-4'''-oxyphenyl) -5 ''-Phenyl-1&quot;, 3 &quot;, 4 &quot; -oxadiazole] -hexyloxy} -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4- Phenylenevinylene, poly {2- [10 '-(2''-(4'''-oxyphenyl) -5 ''-phenyl-1 '', 3 '', 4 ''-oxadiazole) -Decyloxy] -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene, poly {2-methoxy-5- {6 '-[2 `` -4 '''-oxyphenyl)-5''-biphenyl-1'',3'',4''-oxadiazole] -hexyloxy} -1,4-phenylenevinylene- Alt-2,5-didodecyloxy-1,4-phenylenevinylene or poly {2- [10 '-(2''-(4'''-oxyphenyl) -5 ''-biphenyl- 1 '', 3 '', 4 ''-oxadiazole) -decyloxy] -1,4-phenylenevinylene-alt-2,5-didodecyloxy-1,4-phenylenevinylene It is a poly ( p -phenylenevinylene) type organic light emitting polymer characterized by the above-mentioned. (a) the poly ( p -phenylenevinylene) organic light emitting polymer according to any one of claims 1 to 5 as a light emitting layer; (b) a metallic cathode formed on one side of the light emitting layer; And (c) an electroluminescent diode comprising an anode formed on the other side of said light emitting layer. 7. The electroluminescent diode of claim 6, wherein the metallic cathode is selected from the group consisting of Al, In, Al: Li alloys, Mg / Ag, Mg: Ag alloys, Ca / Ag and Ca / Al. The electroluminescent diode of claim 6, wherein the anode is formed by vacuum deposition of indium tin oxide on an organic plastic substrate or glass.