Highly Efficient Poly(p-phenylenevinylene) Derivatives Containing 1,3,4-Oxadiazole Side Group For Po

专利摘要:
A new type of poly (p-phenyl) improves the properties of the electron transport layer by improving the solubility of the light emitting polymer and introducing the 1,3,4-oxadiazole substituent by introducing a substituent which can reduce the light emitting polymer interaction. Lenvinylene) -based light emitting polymers were synthesized. The luminescent polymer was well soluble in general organic solvents, and the polymer thin film could also form an excellent thin film without defects. As a result of the fabrication of single layer type device, the driving voltage is about 4 10 V, and the copolymer of monomer showing electron transporting property and monomer acting as light emitting layer can be formed to improve the characteristics of light emitting device and control emission color than light emitting polymer alone. there was. The maximum luminous intensity and luminous efficiency were about 19500 cd / m2 and 21 cd / A, which showed very good polymer light emitting diode characteristics. English: In order to improve the solubility and electron transport properties of the polymers, a new series of light emitting poly (p-phenylenevinylene) containing the bulky alkyloxy phenyloxy substitutents and 1,3,4-oxadiazole substitutent have been synthesized by Gilch polymerization method . The resulting polymers were soluble in common organic solvents and forming the thin film without defect. Homo- and co-polymers showed the maximum emission peak between 540 and 591 nm according to the various compositions of the comonomers with single layer devices and the turn-onvoltage is about 4-10 V. In order to improve the device performances and tuning the emission colors, we copolymerized the monomer containing the 1,3,4-oxadiazole unit as a pendant group with 1,4-bis (bromomethyl) -2- {2 [(3,7-dimethyloctyl) oxy] phenoxy} benzene. The maximum luminance and luminance efficiency of the present polymers were about 19500 cd / m2 and 21 cd / A.
公开号:KR20020075356A
申请号:KR1020020055266
申请日:2002-09-12
公开日:2002-10-04
发明作者:진성호
申请人:진성호；
IPC主号:

专利说明:

Highly Efficient Poly (p-phenylenevinylene) Derivatives Containing 1, Poly (1,4-phenylenevinylene) -based high efficiency electroluminescent polymer and polymer electroluminescent diode having 1,3,4-oxadiazole and alkoxyphenyloxy substituent 3,4-Oxadiazole Side Group For Polymer Light Emitting Diodes}
[12] The present invention relates to a poly (p-phenylenevinylene) -based electroluminescent polymer and an electron transporting electroluminescent polymer having improved electron transporting properties, a method of manufacturing the same, and an improvement in device characteristics of a light emitting diode. The poly (p-phenylenevinylene) derivative which is a light emitting material of a typical polymer light emitting diode has a problem to be solved as follows.
[13] In the polymerization process, the light emitting polymer completely dissolved in the polymerization solvent and the light emitting polymer in a heterogeneous state in which some precipitates are synthesized at the same time are synthesized. Therefore, the characteristics of the polymer light emitting diode are deteriorated. It is difficult to control the back and also has limitations in mass production.
[14] In the general method of synthesizing poly (p-phenylenevinylene) -based light emitting polymer, sulfonium precursor, which is a precursor of poly (p-phenylenevinylene), takes a very long time to polymerize, yields a very low yield, and consumes a lot of cost. do. And in order to make a complete poly (p-phenylenevinylene) derivative, the sulfonium salt has to be removed, which is difficult to remove completely. In order to be able to operate at a low voltage, the light emitting polymer layer should be formed as a thin film (~ 100 nm). At this time, unreacted sulfonium salt is gradually removed and pinholes are generated, resulting in poor film uniformity and consequently leakage current. While lowering the luminous efficiency. In addition, the synthesis of poly (p-phenylenevinylene) -based light emitting polymers by Wittig reaction, Heck reaction, etc. has a relatively low molecular weight, so that the polymer's ability to form a thin film is lowered and many metal catalysts are used for the polymerization reaction. There is also a problem that the purification process for a number of steps.
[15] Finally, in the case of conventional poly (p-phenylenevinylene) light emitting polymers, hole injection is easier than electron injection, and since hole mobility is much higher than electron mobility, the uniformity of injected holes and electrons As a result, the luminous efficiency is lowered, which makes it difficult to improve the device lifetime of the polymer light emitting diode.
[16] Most poly (p-phenylenevinylene) light emitting polymers synthesize light emitting polymers by various synthesis methods, but the synthesized light emitting polymers are not only synthesized but also lack reproducibility in terms of performance of light emitting diodes. There are some disadvantages that are difficult to increase the purity. In addition, in order to overcome joule heat when driving the light emitting diode, the molecular weight of the thin film should be increased by increasing the molecular weight. In the case of most light emitting polymers, the mobility of holes is much faster than that of electrons, and thus the luminous efficiency is considerably low because many singlet excitons are not formed due to the nonuniformity of holes and electrons. Therefore, in order to improve luminous efficiency, the molecular structure should be designed to facilitate the injection of electrons. Therefore, in the present invention, as a novel luminescent polymer that can solve the disadvantages of the conventional luminescent polymer while maintaining the basic skeleton of poly (p-phenylenevinylene), an improved asymmetric monomer into which an alkoxyphenyloxy substituent having a large steric hindrance is introduced is introduced. Through the polymerization method, new light emitting polymers could be synthesized. In order to synthesize electron transporting light-emitting polymers, the injection of electrons from the cathode is increased by introducing a high electron affinity 1,3,4-oxadiazole-based structure as a side of the light-emitting polymer and increasing the LUMO (Lowest Unoccupied Molecular Orbital) energy level. Designed for ease. In addition, by synthesizing the copolymer, the monomer and the light emitting polymer were designed and synthesized to control the wavelength from green to red in the absorption and emission spectrum by controlling the effective conjugated structure length of the light emitting polymer. In order to achieve the above object, the light emitting polymer of the present invention is represented by the following Chemical Formula 1.
[17] Formula 1
[18] Wherein R is a linear or branched aliphatic alkyl group having 1 to 20 carbon atoms and x is composed of a composition ratio of 0.1 to 1.0.
[19] And a light emitting polymer of the formula was used as a light emitting layer to produce a polymer light emitting diode and the structural formula is shown in Figure 2 below.
[1] 1 is a 1,3,4-oxadiazole system prepared in the present invention Process for manufacturing light emitting polymer diode and light emitting polymer
[2] 2 is a cross-sectional view of the light emitting polymer diode of the present invention.
[3] 3 is a UV-Visible Spectrum of the light emitting polymer films of Examples 10, 11, and 12 of the present invention.
[4] 4 is a Photoluminescence (PL) Spectrum of the light emitting polymer film of Examples 10, 11, 12 of the present invention
[5] 5 is a schematic diagram of energy levels of the light emitting polymer films of Examples 10, 11, and 12 of the present invention.
[6] 6 is an electroluminescence (EL) Spectrum of an ITO / PEDOT / light emitting polymer / Al diode structure employing the light emitting polymers of Examples 10, 11, and 12 of the present invention.
[7] 7 shows the voltage-current density characteristics of an ITO / PEDOT / light emitting polymer / Al diode structure employing the light emitting polymers of Examples 10, 11, and 12 of the present invention.
[8] 8 is a light emission efficiency characteristic of the current of the ITO / PEDOT / light emitting polymer / Al diode structure employing the light emitting polymer of Examples 10, 11, 12 of the present invention
[9] FIG. 9 shows the voltage-luminance intensity characteristics of the ITO / PEDOT / light emitting polymer / Al diode structure employing the light emitting polymers of Examples 10, 11, and 12 of the present invention.
[10] 10 shows ITO / PEDOT / Advertising Molecule / Al diode structure UV, PL EL Spectra using MEH-PPV light emitting polymer of Comparative Example.
[11] Figure 11 shows the voltage-current density characteristics of ITO / PEDOT / LED / Al diode structure using MEH-PPV LED polymer of Comparative Example.
[20] The configuration of the present invention with reference to the accompanying drawings in detail as follows. As mentioned above, the synthesis of electron transporting light emitting polymer for improving luminous efficiency is as follows. In other words, in order to improve electron transport in the poly (p-phenylenevinylene) skeleton, a monomer into which a 1,3,4-oxadiazole substituent is introduced is designed and synthesized, and an electron transporting light emitting polymer is prepared. In addition, the present invention is to prepare a copolymer with a poly (p-phenylenevinylene) -based light emitting polymer having an alkyloxyphenoxy substituent which can serve as a light emitting polymer and control the color of light emitted. First, 4- (2,5-dimethylphenoxy) benzoate was synthesized by reacting 2,5-dimethylphenol and 4-fluoroethylbenzoate and 4- (2,5-dimethylphenoxy) benzohydrazide was synthesized in high yield by reaction with hydrazine. And 4- (3,7-dimethyloctyloxy) benzoyl chloride and 4- (2,5-dimethylphenoxy) benzohydrazide by reacting 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- ( 2,5-diemethylphenoxy) phenyl} -1,3,4-oxadiazole was synthesized and then reacted with SOCl2 to synthesize an intermediate in which the 1,3,4-oxadiazole ring was introduced. Finally, in order to synthesize an electron transporting light emitting monomer, it is brominated using NBS and BPO to cleanly synthesize the final monomer 1,4-bis (bromomethyl) -2- (2- (3,7-dimethylocthyloxy) phenyloxy) benzene. It was. The synthesized monomer was synthesized electron transporting light-emitting polymer by Gilch polymerization method and a copolymer was synthesized to control the light emission characteristics. Representative luminescent polymers thus synthesized are Poly [2- {2-4 '-(3,7-dimethyloctyloxy) phenyloxy} -1,4-phenylenevinylene], [DMOP-PPV], Poly [2- {4- [5- (4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene], [C10PhOxa-PPV] and Poly [2- {4- [5 -(4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene] -co- [2- {2-4 '-(3, 7-dimethyloctyloxy) phenyloxy} -1,4-phenylenevinylene], [C10PhOxa-PPV-co-DMOP-PPV]. Among them, R group substituted by alkyloxyphenyloxy has aliphatic alkoxy (R1) or branched alkoxy (R2) introduced, R1 is (CH2) nCH3, R2 is CH2 (CH2) aCH (CH2) bCH3CH (CH3) 2 and a is 0 B is 0-10, n is an integer of 0-20. And the 1,3,4-oxadiazole substituent is a molecular structure introduced between phenyl and phenyl. The weight average molecular weight distribution (Mw) of the light emitting polymer is about 10,000 to 600,000.
[21] Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
[22] Example 1. Preparation of 4- (2,5-dimethylphenoxy) benzoate (1)
[23] Place a cooling tower in a 250 mL flask with magnetic stirrer bar and add 2,5-dimethylphenol (16.7 g, 0.137 mol) and ethyl 4-fluorobenzoate (23 g, 0.137 mol) to 100 mL of N, N-Dimethylformamide (DMF). Dissolve. And potassium tert-butoxide (18.4 g, 0.164 mol) is added at room temperature and then the reaction proceeds at 150oC for 10 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was added to excess distilled water and extracted several times with diethyl ether. The organic solvent was dried over MgSO4, filtered and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using hexane and dichloromethane (1: 1) as a developing solvent, yielding 4- (2,5-dimethylphenoxy) in a yield of about 68%. It can synthesize benzoate (1).
[24] 1 H NMR (CDCl3, δ ppm): 1.34-1.41 (t, 3H, CH3), 2.12, 2.30 (s, 6H, 2CH3 on aromatic ring), 4.29-4.40 (q, 2H, -OCH2-), 6.79, 6.84- 6.89, 6.92-6.96, 7.13-7.17, 7.96-8.00 (m, 7H, aromatic protons)
[25] Example 2. Preparation of 4- (2,5-dimethylphenoxy) benzohydrazide (2)
[26] A cooling tower was installed in a 250 mL flask with magnetic stirrer bar, and hydrazine monohydrate (26 g, 0.518 mol) was dissolved in 30 mL ethanol. 4- (2,5-dimethylphenoxy) benzoate (20 g, 0.074) synthesized in Example 1 was dissolved. After adding mol), the reaction is performed at 90 ° C. for about 17 hours. After TLC confirmed that 4- (2,5-dimethylphenoxy) benzoate was completely removed from the reaction mixture, the reaction mixture was cooled to room temperature and recrystallized from methanol. The recrystallized compound is washed several times with n-hexane and dried in vacuo to obtain 4- (2,5-dimethylphenoxy) benzohydrazide in a yield of about 75%.
[27] 1 H NMR (CDCl 3, δ ppm): 2.12, 2.30 (s, 6H, 2CH 3 on aromatic ring), 4.0-4.2 (b, 2H, NH 2), 7.2-7.4 (b, 1H, NH), 6.78, 6.84-6.96, 7.13-7.17, 7.65-7.72 (m, 7H, aromatic protons)
[28] Example 3. Preparation of N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide (3)
[29] Place a cooling tower in a 250 mL flask with magnetic stirrer bar, dissolve 4- (2,5-dimethylphenoxy) benzohydrazide (4.4 g, 0.017 mol) and triethylamine (1.74 g, 0.017 mol) in about 50 mL of dichloromethane, and (3,7-dimethyloctyloxy) benzoyl chloride (5.1 g, 0.017 mol) is slowly added dropwise. After stirring the reaction mixture at room temperature for 4 hours, the mixture was extracted with distilled water and dichloromethane, and then the organic solvent was dried over MgSO4, filtered and the solvent was removed by rotary evaporator. After recrystallization with methanol and washing the crystal several times with n-hexane, white crystals of pure N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide were obtained. Obtained in about 97% yield.
[30] 1 H NMR (CDCl 3, δ ppm): 0.84-0.88 (d, 6H, 2CH3) 0.92-0.95 (d, 3H, CH3) 1.16 -1.85 (m, 10H, 4CH2, 2CH) 2.11, 2.30 (s, 6H, 2CH3 on aromatic ring), 3.98-4.05 (t, 2H, OCH2), 6.78-6.96, 7.12-7.16, 7.78-7.83 (m, 11H, aromatic protons), 9.35-9.48 (d, d, 2H, NH)
[31] Example 4. Preparation of 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) phenyl} -1,3,4-oxadiazole (4)
[32] Place a cooling tower in a 250 mL flask with magnetic stirrer bar and add N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide (4 g, 7.74 mmol). Dissolve in mL of benzene. Then add SOCl2 (3.7 g, 30.98 mmol) and react for 4 hours at 120 ° C. After confirming that N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide reacted by TLC, it was cooled to room temperature and the excess solvent and SOCl2 were removed by rotary evaporator. Remove and add the reaction mixture to distilled water and extract with chloroform again. The obtained organic solvent was dried with MgSO 4 and filtered to obtain pure 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) phenyl} -1,3,4 -oxadiazole can be obtained in about 95% yield.
[33] 1 H NMR (CDCl 3, δ ppm): 0.85-0.89 (d, 6H, 2CH 3) 0.94-0.97 (d, 3H, CH 3) 1.18 -1.88 (m, 10H, 4CH 2, 2CH) 2.15, 2.31 (s, 6H, 2CH 3 on aromatic ring), 4.03-4.10 (t, 2H, OCH2), 6.82, 6.93-7.03, 7.14-7.19, 8.01-8.08 (m, 11H, aromatic protons)
[34] Example 5. 2- {4- [2,5-bis (bromomethyl) phenoxy] phenyl-5- {4-[(3,7-dimethyloctyl) oxy] phenyl} -1,3,4-oxadiazole (5) Manufacture
[35] In a 250 mL flask, 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) phenyl} -1,3,4-oxadiazole (5.8 g, 11.6 mmol ), N-bromosuccinimide (4.56 g, 25.6 mmol) and a small amount of benzoyl peroxide are reacted in 100 mL of benzene. Slowly refluxing the reaction mixture yields a white solid, succinimde, which is the starting material 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) starting with TLC. Confirm that phenyl} -1,3,4-oxadiazole is fully reacted, cool, and then filter succinimide. Then, the reaction product was added to distilled water, extracted with dichloromethane, dried over MgSO4, filtered, and separated by n-hexane by column chromatography. Pure 2- {4- [2,5-bis (bromomethyl) phenoxy] phenyl-5- {4- [(3,7-dimethyloctyl) oxy] phenyl} -1,3,4-oxadiazole can be obtained in about 41% yield.
[36] 1 H NMR (CDCl 3, δ ppm): 0.84-0.88 (d, 6H, 2CH 3) 0.93-0.96 (d, 3H, CH 3) 1.17 -1.88 (m, 10H, 4CH 2, 2CH) 4.06-4.12 (t, 2H, OCH 2) , 4.40, 4.54 (s, 4H, 2CH2Br on aromatic ring), 6.97-7.03, 7.11-7.21, 7.43-7.48, 8.01-8.14 (m, 11H, aromatic protons)
[37] Example 6. Preparation of 2- (2-Methoxyphenyloxy) -1,4-dimethylbenzene (6)
[38] Add crushed KOH (8.98 g, 0.16 mol) to a 250 mL flask and slowly add Guaiacol (20 g, 0.16 mol) to it while stirring with a magnetic bar. Since this reaction is exothermic, it is performed at room temperature. When Guaiacol enters, the reaction becomes solid and the color turns to light gray. After the guaiacol is added, the reaction mixture is stirred for 3 to 4 hours while heating to 150C in an oil bath. After the reaction, the resultant is overnight under reduced pressure at 150C to remove the water obtained as a by-product. After that, potassium o-methoxyphenoxide is dark grey. Add a small amount of Cu as a catalyst to 2-bromo-p-xylene (20 ml, 0.15mol) and a few drops of Guaiacol and reflux while stirring at 200C. The reaction occurs at around 190C and the state is liquefied and turns black. After the reaction for about 5 hours, the mixture is cooled and extracted with water and excess ether. The organic solution obtained by extraction is dried over anhydrous MgSO 4, filtered and the solvent is removed. The solution thus obtained is purified by vacuum distillation or column chromatography (silicagel, eluent: hexanaethyl ethyl acetate (10: 1)). The yield was 70% and the structure was confirmed by 1 H-NMR.
[39] 1 H-NMR (CDCl 3): 2.25 (s, 6H, 2CH 3 on aromatic ring), 3.9 (s, 3H, -OCH 3), 6.6-7.2 (m, 7H, aromatic protons).
[40] Example 7. Preparation of 2- (2-Hydroxyphenoxy) -1,4-dimethylbenzene (7)
[41] Methylene chloride (250 ml) was added to a 500 mL flask as a solvent, and the solution (23 g, 0.1 mol) synthesized in Example 6 was added thereto. Cool to 0C in an ice bath and stir after installing the cooling tower. AlCl 3 (66 g, 0.5 mol) was added thereto, and S (CH 3) 2 (38.6 g, 0.62 mol) was slowly added, followed by reaction at 0C for about 2 hours. At the end of the reaction, the reaction is placed in a 1 L beaker containing an appropriate amount of aqueous NH 4 Cl solution and ice. The organic layer was extracted with water and ether, anhydrous MgSO 4 was added, dried, filtered and the solvent was removed. The reaction mixture thus obtained was identified by TLC (eluent: hexane / ethyl acetate (9: 1)), and the product (2) was purified by column chromatography (silicagel, eluent: hexane / ethyl acetate (9: 1)). The yield is more than 95% and the structure was confirmed by 1H-NMR.
[42] 1 H-NMR (CDCl 3): 2.20, 2.25 (s, 6H, 2CH 3 on aromatic ring), 5.7 (s, H, -OH), 6.6-7.2 (m, 7H, aromatic protons).
[43] Example 8. Preparation of 2- (2- (3,7-Dimethylocthyl) oxy) phenyloxy-1,4-dimethylbenzene (8)
[44] 250 ml of methylene chloride as a solvent was added to a 500 mL flask, and the compound synthesized in Example 7 (19.5 g, 0.09 mol), KOH (5.62 g, 0.1 mol), 3,7-dimethylocthyl bromide (24.21 g, 0.11 mol), and a catalyst were prepared. Add a small amount of KI and stir for 24 hours with reflux. The reaction product is extracted with water and ether, and the organic layer is taken, anhydrous MgSO 4 is added, dried, filtered and the solvent is removed in vacuo. This reaction mixture purifies 2- (2- (3,7-dimethylocthyloxy) phenyloxy) -1,4-dimethylbenzene through vacuum distillation and column chromatography (silica gel, eluent: hexane / ethyl acetate (10: 1)). . The yield is more than 70% and the structure was confirmed by 1H-NMR.
[45] 1 H-NMR (CDCl 3): 2.2, 2.25 (s, 6H, 2CH 3 on aromatic ring), 0.8-1.6 (m, 19H, CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 4.0 (t, 2H, − OCH2-), 6.5-7.2 (m, 7H, aromatic protons).
[46] Example 9 Preparation of 1,4-Bis (bromomethyl) -2- (2- (3,7-dimethylocthyloxy) phenyloxy) benzene (9)
[47] In a 500 mL flask, add 200 ml of solvent CCl4 (22 g, 0.06 mol) and the small amount of BPO (benzoyl peroxide) and NBS (N-Bromosuccinimide) (25 g, 0.14 mol) as the radical initiator. Stir for about 6 hours. This produces a white solid that is the succinimide that NBS reacts to. After the reaction, the solution is filtered to remove it and extracted with water and chloroform. The organic solution obtained by extraction is dried over anhydrous MgSO 4, filtered and the solvent is removed in vacuo. The concentrated mixture was purified by column chromatography (silica gel, eluent: hexane / methylene chloride (4: 1)) using 1,4-Bis (bromomethyl) -2- (2- (3,7-dimethylocthyloxy) phenyloxy) Purify benzene. Yield is about 25% and the structure was confirmed by 1H-NMR.
[48] 1 H-NMR (CDCl 3): 0.8-1.6 (m, 19H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 4.0 (t, 2H, -OCH 2-), 4.35, 4.7 (s, 4H, 2CH 2 Br on aromatic ring), 6.6-7.4 (m, 7H, aromatic protons).
[49] Example 10. poly [2- {4- [5- (4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene] (10 ), Production of Oxa-PPV
[50] While stirring the 100 mL polymerization flask with a magnetic bar, repeat the procedure under reduced pressure and reflux with nitrogen three times to remove the moisture in the flask. After the water was removed, the monomer (0.3 g, 0.46 mmol) synthesized in Example 5 was added thereto, and the mixture was refluxed twice with reduced pressure and nitrogen, and then 30 mL of anhydrous toluene was added thereto as a solvent. Add potassium tert-butoxide (1.0M / THF) at 0C slowly with syringe pump for 30 minutes with stirring, and after stirring for 4 hours at room temperature, terminate the polymerization and neutralize the polymer terminal. Add about 0.5ml of 4- [5- (bromomethyl) -2-methylphenoxy] phenyl} -5- {4-[(3,7-dimethyloctyl) oxy] phenyl} -1,3,4-oxadiazole for about 1 hour Stir again. The polymerization product was precipitated in a large amount of methanol, filtered through thimble, and soxhleted with methanol to remove low molecular weight oligomers and impurities. Concentrate the polymer solution obtained by Soxhlet again with chloroform, reprecipitate in methanol once again, filter and dry under vacuum to obtain the final polymer. The yield is more than 60% and the structure was confirmed by 1H-NMR.
[51] 1 H NMR (CDCl 3, δ): 0.72-1.80 (m, 19H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 3.90-4.12 (br, 2H, -OCH 2), 6.55-7.40, 7.80-8.15 (br, 13H, aromatic protons and vinylic protons).
[52] Example 11 Preparation of Poly [2- (2- (3,7-dimethylocthyloxy) phenyloxy) -1,4-phenylenevinylene] (11), Preparation of (DMOP-PPV)
[53] While stirring the 100 mL polymerization flask with a magnetic bar, repeat the procedure under reduced pressure and reflux with nitrogen three times to remove the moisture in the flask. After the water was removed, the monomer (0.2 g, 0.39 mmol) synthesized in Example 9 was added thereto, and the mixture was refluxed twice with reduced pressure and nitrogen, and then 30 mL of anhydrous THF was added thereto as a solvent. 2.34ml of potassium tert-butoxide (1.0M / THF) at 0C was added slowly by syringe pump for 30 minutes and stirred at room temperature for 3 hours, followed by 4- (tert to terminate the polymerization reaction and neutralize the polymer terminal. Add 0.5 ml of benzyl bromide and stir again for about 1 hour. The reactant was precipitated in a large amount of methanol, filtered through thimble, and soxhletized with methanol to remove low molecular weight oligomers and impurities. Concentrate the polymer solution obtained by Soxhlet again with chloroform, reprecipitate in methanol once again, filter and dry under vacuum to obtain the final polymer. The yield is more than 60% and the structure was confirmed by 1H-NMR.
[54] 1 H-NMR (CDCl 3): 0.8-1.8 (m, 19H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 3.95 (br, 2H, -OCH 2-), 6.6-7.7 (m, 9H, aromatic protons and vinylic protons).
[55] Example 12. Poly [2- {4- [5- (4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene] -co -[2- (2- (3,7-dimethylocthyloxy) phenyloxy) -1,4-phenylenevinylene] (12) Preparation, Preparation of Oxa-PPV-co-DMOP-PPV
[56] The monomers (5) and (10) prepared in Examples 5 and 9 were removed while controlling various molar composition ratios (90:10, 70:30, 50:50, 30:70, 10:90 mol%). Dissolved in THF (monomer concentration: 1 wt%) and stirred at the polymerization temperature of room temperature with potassium tert- butoxide (1.0 M THF solution, about 6 equivalents to monomer) using a syringe pump for 30 minutes. Drop it slowly. When the amount of potassium tert- butoxide begins to exceed 1.5-2.0 equivalents, the viscosity of the solution increases and a strong fluorescence begins to appear. After stirring for 3 hours at the polymerization temperature 2- {4- [5- (bromomethyl) -2-methylphenoxy] phenyl} -5- {4-[(3,7-dimethyloctyl) oxy] phenyl} -1 in a polymerization reactor A small amount of, 3,4-oxadiazole is added and stirred for 1 hour to remove the reactivity of the light emitting polymer terminal. The polymer mixture is reprecipitated in a large amount of methanol or isopropylalcohol. The obtained polymer is removed using a Soxhlet apparatus to remove the low molecular weight oligomer and catalyst, and then reprecipitated in methanol to obtain a final light emitting copolymer polymer by drying. (Yield 70%). The weight average molecular weight of the obtained polymer is about 3.8 to 5.9x105 and the polydispersity is about 4.8 to 8.6 . The structure and composition ratio were confirmed by 1H-NMR .
[57] 1 H NMR (CDCl 3, δ): 0.82-1.80 (m, 38H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 3.90-4.12 (br, 2H, -OCH 2), 3.80-4.05 (br, 2H , -OCH2-) 6.55-7.75, 7.82-8.15 (m, 22H, aromatic protons and vinylic protons)
[58] Example 13. Molecular Weight Cutting Method and Membrane Purification Process Using Membrane Filter
[59] Oxa-PPV and DMOP-PPV and the copolymer Oxa-PPV-co-DMOP-PPV, which are synthesized in Examples 10, 11, and 12, were dissolved in a small amount of chloroform, followed by a membrane tube made of Spectrum's polyvinylidene fluoride (PVDF). Put it in. The membrane tube was placed in a 1 L beaker containing 800 mL of chloroform, and the low molecular weight polymer was removed by osmotic pressure for about 7 days while stirring with a magnetic bar. The luminescent polymer in the membrane tube is precipitated in methanol again, filtered and dried to obtain highly purified luminescent polymer.
[60] Example 14 UV-visible, Photoluminescence (PL) Spectrum Characteristics of Light-Emitting Polymer Films
[61] After the light emitting polymer solutions synthesized in Examples 10, 11, and 12 were spin coated onto a glass substrate to form a polymer thin film, UV absorption peaks and photoluminescence (PL) spectra were measured. UV maximum absorption peaks of Oxa-PPV, DMOP-PPV, and Oxa-PPV-co-DMOP-PPV were generally found at 441, 303 nm, 454 nm and 570 nm, respectively, depending on the composition ratio. When the 1,3,4-oxadiazole substituent with high electron affinity is introduced, a characteristic peak of 1,3,4-oxadiazole is shown at about 303 nm, but the peak at 303 nm also decreases as the content of oxadiazole in the copolymer decreases. It can be seen. The PL spectrum was measured by using the maximum absorption wavelength of each of the light emitting polymers as the excitation wavelength. In the case of Oxa-PPV, the maximum PL peak and the shoulder at 542 nm were observed at 573 mn, and DMOP-PPV at the maximum PL peak at 539 nm and 520 nm. shoulder was measured. It was found that the Oxa-PPV-co-DMOP-PPV copolymer shifted to a longer wavelength than the maximum emission peak of DMOP-PPV alone as the content of Oxa-PPV increased. In addition, the luminescence phenomenon generated by the 1,3,4-oxadiazole substituent in the PL spectrum was not observed, and thus, it can be seen that an effective energy transfer occurs from the 1,3,4-oxadiazole substituent to the PPV light emitting polymer skeleton.
[62] Example 15. Fabrication of Electroluminescent Device
[63] An electroluminescent device was manufactured using the light emitting polymers Oxa-PPV and DMOP-PPV prepared in Examples 10, 11 and 12 and Oxa-PPV-co-DMOP-PPV which is a copolymerized light emitting polymer. The structure of the fabricated electroluminescent device is shown in FIG. The manufacturing process of the electroluminescent device is to clean the transparent electrode substrate coated with ITO (indium-tinoxide) on the glass substrate, and then ITO glass using a photoresist resign and an etchant using a microprocessing process After the formation, it was washed again. The driving voltage and the luminous efficiency are greatly influenced by the uniformity of the surface of the ITO, the adhesion ability between the electrode and the light emitting polymer interface, and the balance of the carriers (holes and electrons). To solve this problem, PEDOT, a conductive polythiophene derivative, was coated with a thickness of about 100 μs as a hole injection layer and baked at 110 ° C. for about 10 minutes. The light emitting polymer solution prepared by dissolving in chlorobenzene was spin coated on the hole injection layer, and after baking, the solvent was completely removed in a vacuum oven to form a polymer thin film. The polymer solution was spin coated by filtering with a 0.2 μm filter, and the polymer thin film thickness can be freely controlled by adjusting the concentration and spin rate of the polymer solution. The light emitting polymer thickness is about 80-200 nm. In addition, Al, a cathode electrode capable of injecting electrons, was deposited by using a vacuum vaporizer (thermoevaporator) while maintaining a vacuum degree of 4 × 10 −6 torr or less. During deposition, the film thickness and growth rate were controlled by using a crystal sensor. The emission area was 4 ㎜ and the driving voltage was a direct bias voltage.
[64] Example 16. Electroluminescence (EL) Spectrum Measurement and Electro-optical Characterization
[65] The electroluminescent properties of the polymer electroluminescent diode fabricated in Example 15 were evaluated. The monolayer electroluminescent devices of the fabricated ITO / PEDOT / Polymer / Al structure showed typical diode characteristics. In the case of Oxa-PPV, DMOP-PPV and copolymerized light-emitting polymer, Oxa-PPV-co-DMOP-PPV, the driving voltage started at about 4-10 V (Fig. 7) and the amount of carriers injected increased as the voltage increased. As a result, the current density also increased exponentially. The driving voltage of DMOP-PPV is lower than that of Oxa-PPV because the DMOP-PPV is smaller than the HOMO energy level of Oxa-PPV at the HOMO energy level of each light emitting polymer. Because it is easy. In the copolymer, Oxa-PPV-co-DMOP-PPV, the HOMO energy level of the copolymer is similar to that of Oxa-PPV. Oxa-PPV has a role of significantly increasing the LUMO energy level by introducing 1,3,4-oxadiazole substituent which has excellent electron affinity. Accordingly, as the 1,3,4-oxadiazole content was increased in the luminescent polymer energy level diagram of FIG. 5, the LUMO energy levels of the copolymers Oxa-PPV-co-DMOP-PPV and Oxa-PPV increased significantly. It can be seen from FIG. 8 that the injection of electrons from the cathode occurs easily and thus the balance between injected holes and electrons is achieved, resulting in a rapid increase in luminous efficiency. 9 shows the intensity of light emission luminance with respect to an applied voltage. The maximum luminous efficiency and luminous luminance are about 21.1 cd / A and 19500 cd / m2.
[66] Example 17. Comparative Example with MEH-PPV
[67] The following comparative example compared the electro-optical characteristics when using MEH-PPV. FIG. 10 shows the emission spectrum (EL) measured by fixing the voltage at 10 V and emits light in the red region. 11 is a diagram showing a correlation between current and voltage when MEH-PPV is used as a light emitting layer. It can be seen that the current gradually flows at about 3 V in the driving voltage.
[68] The configuration of the present invention with reference to the accompanying drawings in detail as follows. As mentioned above, the synthesis of electron transporting light emitting polymer for improving luminous efficiency is as follows. In other words, in order to improve electron transport in the poly (p-phenylenevinylene) skeleton, a monomer into which a 1,3,4-oxadiazole substituent is introduced is designed and synthesized, and an electron transporting light emitting polymer is prepared. In addition, the present invention is to prepare a copolymer with a poly (p-phenylenevinylene) -based light emitting polymer having an alkyloxyphenoxy substituent which can serve as a light emitting polymer and control the color of light emitted. First, 4- (2,5-dimethylphenoxy) benzoate was synthesized by reacting 2,5-dimethylphenol and 4-fluoroethylbenzoate and 4- (2,5-dimethylphenoxy) benzohydrazide was synthesized in high yield by reaction with hydrazine. And 4- (3,7-dimethyloctyloxy) benzoyl chloride and 4- (2,5-dimethylphenoxy) benzohydrazide by reacting 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- ( 2,5-diemethylphenoxy) phenyl} -1,3,4-oxadiazole was synthesized and then reacted with SOCl2 to synthesize an intermediate in which the 1,3,4-oxadiazole ring was introduced. Finally, in order to synthesize an electron transporting light emitting monomer, it is brominated using NBS and BPO to cleanly synthesize the final monomer 1,4-bis (bromomethyl) -2- (2- (3,7-dimethylocthyloxy) phenyloxy) benzene. It was. The synthesized monomer was synthesized electron transporting light-emitting polymer by Gilch polymerization method and a copolymer was synthesized to control the light emission characteristics. Representative luminescent polymers thus synthesized are Poly [2- {2-4 '-(3,7-dimethyloctyloxy) phenyloxy} -1,4-phenylenevinylene], [DMOP-PPV], Poly [2- {4- [5- (4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene], [C10PhOxa-PPV] and Poly [2- {4- [5 -(4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene] -co- [2- {2-4 '-(3, 7-dimethyloctyloxy) phenyloxy} -1,4-phenylenevinylene], [C10PhOxa-PPV-co-DMOP-PPV]. Among them, R group substituted by alkyloxyphenyloxy has aliphatic alkoxy (R1) or branched alkoxy (R2) introduced, R1 is (CH2) nCH3, R2 is CH2 (CH2) aCH (CH2) bCH3CH (CH3) 2 and a is 0 B is 0-10, n is an integer of 0-20. And the 1,3,4-oxadiazole substituent is a molecular structure introduced between phenyl and phenyl. The weight average molecular weight distribution (Mw) of the light emitting polymer is about 10,000 to 600,000.
[69] Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
[70] Example 1. Preparation of 4- (2,5-dimethylphenoxy) benzoate (1)
[71] Place a cooling tower in a 250 mL flask with magnetic stirrer bar and add 2,5-dimethylphenol (16.7 g, 0.137 mol) and ethyl 4-fluorobenzoate (23 g, 0.137 mol) to 100 mL of N, N-Dimethylformamide (DMF). Dissolve. And potassium tert-butoxide (18.4 g, 0.164 mol) is added at room temperature and then the reaction proceeds at 150oC for 10 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was added to excess distilled water and extracted several times with diethyl ether. The organic solvent was dried over MgSO4, filtered and the solvent was removed using a rotary evaporator. The solvent was separated by column chromatography using hexane and dichloromethane (1: 1) as a developing solvent, yielding 4- (2,5-dimethylphenoxy) in a yield of about 68%. It can synthesize benzoate (1).
[72] 1 H NMR (CDCl3, δ ppm): 1.34-1.41 (t, 3H, CH3), 2.12, 2.30 (s, 6H, 2CH3 on aromatic ring), 4.29-4.40 (q, 2H, -OCH2-), 6.79, 6.84- 6.89, 6.92-6.96, 7.13-7.17, 7.96-8.00 (m, 7H, aromatic protons)
[73] Example 2. Preparation of 4- (2,5-dimethylphenoxy) benzohydrazide (2)
[74] A cooling tower was installed in a 250 mL flask with magnetic stirrer bar, and hydrazine monohydrate (26 g, 0.518 mol) was dissolved in 30 mL ethanol. 4- (2,5-dimethylphenoxy) benzoate (20 g, 0.074) synthesized in Example 1 was dissolved. After adding mol), the reaction is performed at 90 ° C. for about 17 hours. After TLC confirmed that 4- (2,5-dimethylphenoxy) benzoate was completely removed from the reaction mixture, the reaction mixture was cooled to room temperature and recrystallized from methanol. The recrystallized compound is washed several times with n-hexane and dried in vacuo to obtain 4- (2,5-dimethylphenoxy) benzohydrazide in a yield of about 75%.
[75] 1 H NMR (CDCl 3, δ ppm): 2.12, 2.30 (s, 6H, 2CH 3 on aromatic ring), 4.0-4.2 (b, 2H, NH 2), 7.2-7.4 (b, 1H, NH), 6.78, 6.84-6.96, 7.13-7.17, 7.65 -7.72 (m, 7H, aromatic protons)
[76] Example 3. Preparation of N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide (3)
[77] Place a cooling tower in a 250 mL flask with magnetic stirrer bar, dissolve 4- (2,5-dimethylphenoxy) benzohydrazide (4.4 g, 0.017 mol) and triethylamine (1.74 g, 0.017 mol) in about 50 mL of dichloromethane, and (3,7-dimethyloctyloxy) benzoyl chloride (5.1 g, 0.017 mol) is slowly added dropwise. After stirring the reaction mixture at room temperature for 4 hours, the mixture was extracted with distilled water and dichloromethane, and then the organic solvent was dried over MgSO4, filtered and the solvent was removed by rotary evaporator. After recrystallization with methanol and washing the crystal several times with n-hexane, white crystals of pure N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide were obtained. Obtained in about 97% yield.
[78] 1 H NMR (CDCl 3, δ ppm): 0.84-0.88 (d, 6H, 2CH3) 0.92-0.95 (d, 3H, CH3) 1.16 -1.85 (m, 10H, 4CH2, 2CH) 2.11, 2.30 (s, 6H, 2CH3 on aromatic ring), 3.98-4.05 (t, 2H, OCH2), 6.78-6.96, 7.12-7.16, 7.78-7.83 (m, 11H, aromatic protons), 9.35-9.48 (d, d, 2H, NH)
[79] Example 4. Preparation of 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) phenyl} -1,3,4-oxadiazole (4)
[80] Install a cooling tower in a 250 mL flask with magnetic stirrer bar and add N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide (4 g, 7.74 mmol). Dissolve in mL of benzene. Then add SOCl2 (3.7 g, 30.98 mmol) and react for 4 hours at 120 ° C. After confirming that N- {4-[(3,7-dimethyloctyl) oxy] benzoyl} -4- (2,3-diemethylphenoxy) benzohydrazide reacted by TLC, it was cooled to room temperature and the excess solvent and SOCl2 were removed by rotary evaporator. Remove and add the reaction mixture to distilled water and extract with chloroform again. The obtained organic solvent was dried with MgSO 4 and filtered to obtain pure 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) phenyl} -1,3,4 -oxadiazole can be obtained in about 95% yield.
[81] 1 H NMR (CDCl 3, δ ppm): 0.85-0.89 (d, 6H, 2CH 3) 0.94-0.97 (d, 3H, CH 3) 1.18 -1.88 (m, 10H, 4CH 2, 2CH) 2.15, 2.31 (s, 6H, 2CH 3 on aromatic ring), 4.03-4.10 (t, 2H, OCH2), 6.82, 6.93-7.03, 7.14-7.19, 8.01-8.08 (m, 11H, aromatic protons)
[82] Example 5. 2- {4- [2,5-bis (bromomethyl) phenoxy] phenyl-5- {4-[(3,7-dimethyloctyl) oxy] phenyl} -1,3,4-oxadiazole (5) Manufacture
[83] In a 250 mL flask, 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy) phenyl} -1,3,4-oxadiazole (5.8 g, 11.6 mmol ), N-bromosuccinimide (4.56 g, 25.6 mmol) and a small amount of benzoyl peroxide are reacted in 100 mL of benzene. When the reaction mixture was slowly refluxed, a white solid, succinimde was formed, and TLC was used as a starting material, 2- {4-[(3,7-dimethyloctyl) oxy] phenyl} -5- {4- (2,5-diemethylphenoxy). Confirm that phenyl} -1,3,4-oxadiazole is fully reacted, cool, and then filter succinimide. Then, the reaction product was added to distilled water, extracted with dichloromethane, dried over MgSO4, filtered, and separated by n-hexane by column chromatography. Pure 2- {4- [2,5-bis (bromomethyl) phenoxy] phenyl-5- {4- [(3,7-dimethyloctyl) oxy] phenyl} -1,3,4-oxadiazole can be obtained in about 41% yield.
[84] 1 H NMR (CDCl 3, δ ppm): 0.84-0.88 (d, 6H, 2CH 3) 0.93-0.96 (d, 3H, CH 3) 1.17 -1.88 (m, 10H, 4CH 2, 2CH) 4.06-4.12 (t, 2H, OCH 2) , 4.40, 4.54 (s, 4H, 2CH2Br on aromatic ring), 6.97-7.03, 7.11-7.21, 7.43-7.48, 8.01-8.14 (m, 11H, aromatic protons)
[85] Example 6. Preparation of 2- (2-Methoxyphenyloxy) -1,4-dimethylbenzene (6)
[86] Add crushed KOH (8.98 g, 0.16 mol) to a 250 mL flask and slowly add Guaiacol (20 g, 0.16 mol) to it while stirring with a magnetic bar. Since this reaction is exothermic, it is performed at room temperature. When Guaiacol enters, the reaction becomes solid and the color turns to light gray. After the guaiacol is added, the reaction mixture is stirred for 3 to 4 hours while heating to 150C in an oil bath. After the reaction, the resultant is overnight under reduced pressure at 150C to remove the water obtained as a by-product. After that, potassium o-methoxyphenoxide is dark grey. Add a small amount of Cu as a catalyst to 2-bromo-p-xylene (20 ml, 0.15 mol) and a few drops of Guaiacol and reflux while stirring at 200C. The reaction occurs at around 190C and the state is liquefied and turns black. After the reaction for about 5 hours, the mixture is cooled and extracted with water and excess ether. The organic solution obtained by extraction is dried over anhydrous MgSO 4, filtered and the solvent is removed. The solution thus obtained is purified by vacuum distillation or column chromatography (silicagel, eluent: hexanaethyl ethyl acetate (10: 1)). The yield was 70% and the structure was confirmed by 1 H-NMR.
[87] 1 H-NMR (CDCl 3): 2.25 (s, 6H, 2CH 3 on aromatic ring), 3.9 (s, 3H, -OCH 3), 6.6-7.2 (m, 7H, aromatic protons).
[88] Example 7. Preparation of 2- (2-Hydroxyphenoxy) -1,4-dimethylbenzene (7)
[89] Methylene chloride (250 ml) was added to a 500 mL flask as a solvent, and the solution (23 g, 0.1 mol) synthesized in Example 6 was added thereto. Cool to 0C in an ice bath and stir after installing the cooling tower. AlCl 3 (66 g, 0.5 mol) was added thereto, and S (CH 3) 2 (38.6 g, 0.62 mol) was slowly added, followed by reaction at 0C for about 2 hours. At the end of the reaction, the reaction is placed in a 1 L beaker containing an appropriate amount of aqueous NH 4 Cl solution and ice. The organic layer was extracted with water and ether, anhydrous MgSO 4 was added, dried, filtered and the solvent was removed. The reaction mixture thus obtained was identified by TLC (eluent: hexane / ethyl acetate (9: 1)), and the product (2) was purified by column chromatography (silicagel, eluent: hexane / ethyl acetate (9: 1)). The yield is more than 95% and the structure was confirmed by 1H-NMR.
[90] 1 H-NMR (CDCl 3): 2.20, 2.25 (s, 6H, 2CH 3 on aromatic ring), 5.7 (s, H, -OH), 6.6-7.2 (m, 7H, aromatic protons).
[91] Example 8. Preparation of 2- (2- (3,7-Dimethylocthyl) oxy) phenyloxy-1,4-dimethylbenzene (8)
[92] 250 ml of methylene chloride as a solvent was added to a 500 mL flask, and the compound synthesized in Example 7 (19.5 g, 0.09 mol), KOH (5.62 g, 0.1 mol), 3,7-dimethylocthyl bromide (24.21 g, 0.11 mol), and a catalyst were prepared. Add a small amount of KI and stir for 24 hours with reflux. The reaction product is extracted with water and ether, and the organic layer is taken, anhydrous MgSO 4 is added, dried, filtered and the solvent is removed in vacuo. This reaction mixture purifies 2- (2- (3,7-dimethylocthyloxy) phenyloxy) -1,4-dimethylbenzene through vacuum distillation and column chromatography (silica gel, eluent: hexane / ethyl acetate (10: 1)). . The yield is more than 70% and the structure was confirmed by 1H-NMR.
[93] 1 H-NMR (CDCl 3): 2.2, 2.25 (s, 6H, 2CH 3 on aromatic ring), 0.8-1.6 (m, 19H, CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 4.0 (t, 2H, − OCH2-), 6.5-7.2 (m, 7H, aromatic protons).
[94] Example 9 Preparation of 1,4-Bis (bromomethyl) -2- (2- (3,7-dimethylocthyloxy) phenyloxy) benzene (9)
[95] In a 500 mL flask, add 200 ml of solvent CCl4 (22 g, 0.06 mol) and the small amount of BPO (benzoyl peroxide) and NBS (N-Bromosuccinimide) (25 g, 0.14 mol) as the radical initiator. Stir for about 6 hours. This produces a white solid that is the succinimide that NBS reacts to. After the reaction, the solution is filtered to remove it and extracted with water and chloroform. The organic solution obtained by extraction is dried over anhydrous MgSO 4, filtered and the solvent is removed in vacuo. The concentrated mixture was purified by column chromatography (silica gel, eluent: hexane / methylene chloride (4: 1)) using 1,4-Bis (bromomethyl) -2- (2- (3,7-dimethylocthyloxy) phenyloxy) Purify benzene. Yield is about 25% and the structure was confirmed by 1H-NMR.
[96] 1 H-NMR (CDCl 3): 0.8-1.6 (m, 19H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 4.0 (t, 2H, -OCH 2-), 4.35, 4.7 (s, 4H, 2CH 2 Br on aromatic ring), 6.6-7.4 (m, 7H, aromatic protons).
[97] Example 10. poly [2- {4- [5- (4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene] (10 ), Production of Oxa-PPV
[98] While stirring the 100 mL polymerization flask with a magnetic bar, repeat the procedure under reduced pressure and reflux with nitrogen three times to remove the moisture in the flask. After the water was removed, the monomer (0.3 g, 0.46 mmol) synthesized in Example 5 was added thereto, and the mixture was refluxed twice with reduced pressure and nitrogen, and then 30 mL of anhydrous toluene was added thereto as a solvent. Add potassium tert-butoxide (1.0M / THF) at 0C slowly with syringe pump for 30 minutes with stirring, and after stirring for 4 hours at room temperature, terminate the polymerization and neutralize the polymer terminal. Add about 0.5ml of 4- [5- (bromomethyl) -2-methylphenoxy] phenyl} -5- {4-[(3,7-dimethyloctyl) oxy] phenyl} -1,3,4-oxadiazole for about 1 hour Stir again. The polymerization product was precipitated in a large amount of methanol, filtered through thimble, and soxhleted with methanol to remove low molecular weight oligomers and impurities. Concentrate the polymer solution obtained by Soxhlet again with chloroform, reprecipitate in methanol once again, filter and dry under vacuum to obtain the final polymer. The yield is more than 60% and the structure was confirmed by 1H-NMR.
[99] 1 H NMR (CDCl 3, δ): 0.72-1.80 (m, 19H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 3.90-4.12 (br, 2H, -OCH 2), 6.55-7.40, 7.80-8.15 (br, 13H, aromatic protons and vinylic protons).
[100] Example 11 Preparation of Poly [2- (2- (3,7-dimethylocthyloxy) phenyloxy) -1,4-phenylenevinylene] (11), Preparation of (DMOP-PPV)
[101] While stirring the 100 mL polymerization flask with a magnetic bar, repeat the procedure under reduced pressure and reflux with nitrogen three times to remove the moisture in the flask. After the water was removed, the monomer (0.2 g, 0.39 mmol) synthesized in Example 9 was added thereto, and the mixture was refluxed twice with reduced pressure and nitrogen, and then 30 mL of anhydrous THF was added thereto as a solvent. 2.34ml of potassium tert-butoxide (1.0M / THF) at 0C was added slowly by syringe pump for 30 minutes and stirred at room temperature for 3 hours, followed by 4- (tert to terminate the polymerization reaction and neutralize the polymer terminal. Add 0.5 ml of benzyl bromide and stir again for about 1 hour. The reactant was precipitated in a large amount of methanol, filtered through thimble, and soxhletized with methanol to remove low molecular weight oligomers and impurities. Concentrate the polymer solution obtained by Soxhlet again with chloroform, reprecipitate in methanol once again, filter and dry under vacuum to obtain the final polymer. The yield is more than 60% and the structure was confirmed by 1H-NMR.
[102] 1 H-NMR (CDCl 3): 0.8-1.8 (m, 19H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 3.95 (br, 2H, -OCH 2-), 6.6-7.7 (m, 9H, aromatic protons and vinylic protons).
[103] Example 12. Poly [2- {4- [5- (4- (3,7-dimethyloctyloxy) phenyl) -1,3,4-oxadiazole-2-yl] phenyloxy} -1,4-phenylenevinylene] -co -[2- (2- (3,7-dimethylocthyloxy) phenyloxy) -1,4-phenylenevinylene] (12) Preparation, Preparation of Oxa-PPV-co-DMOP-PPV
[104] The monomers (5) and (10) prepared in Examples 5 and 9 were removed while controlling various molar composition ratios (90:10, 70:30, 50:50, 30:70, 10:90 mol%). Dissolved in THF (monomer concentration: 1 wt%) and stirred at the polymerization temperature of room temperature with potassium tert- butoxide (1.0 M THF solution, about 6 equivalents to monomer) using a syringe pump for 30 minutes. Drop it slowly. As the amount of potassium tert- butoxide begins to exceed 1.5-2.0 equivalents, the viscosity of the solution increases and a strong fluorescence begins to develop. After stirring for 3 hours at the polymerization temperature 2- {4- [5- (bromomethyl) -2-methylphenoxy] phenyl} -5- {4-[(3,7-dimethyloctyl) oxy] phenyl} -1 in a polymerization reactor A small amount of, 3,4-oxadiazole is added and stirred for 1 hour to remove the reactivity of the light emitting polymer terminal. The polymer mixture is reprecipitated in a large amount of methanol or isopropylalcohol. The obtained polymer is removed using a Soxhlet apparatus to remove the low molecular weight oligomer and catalyst, and then reprecipitated in methanol to obtain a final light emitting copolymer polymer by drying. (Yield 70%). The weight average molecular weight of the obtained polymer is about 3.8 to 5.9x105 and the polydispersity is about 4.8 to 8.6 . The structure and composition ratio were confirmed by 1H-NMR .
[105] 1 H NMR (CDCl 3, δ): 0.82-1.80 (m, 38H, -CH 2 CH (CH 3) (CH 2) 3 CH (CH 3) 2), 3.90-4.12 (br, 2H, -OCH 2), 3.80-4.05 (br, 2H , -OCH2-) 6.55-7.75, 7.82-8.15 (m, 22H, aromatic protons and vinylic protons)
[106] Example 13. Molecular Weight Cutting Method and Membrane Purification Process Using Membrane Filter
[107] Oxa-PPV and DMOP-PPV and the copolymer Oxa-PPV-co-DMOP-PPV, which are synthesized in Examples 10, 11, and 12, were dissolved in a small amount of chloroform, followed by a membrane tube made of Spectrum's polyvinylidene fluoride (PVDF). Put it in. The membrane tube was placed in a 1 L beaker containing 800 mL of chloroform, and the low molecular weight polymer was removed by osmotic pressure for about 7 days while stirring with a magnetic bar. The luminescent polymer in the membrane tube is precipitated in methanol again, filtered and dried to obtain highly purified luminescent polymer.
[108] Example 14 UV-visible, Photoluminescence (PL) Spectrum Characteristics of Light-Emitting Polymer Films
[109] After the light emitting polymer solutions synthesized in Examples 10, 11, and 12 were spin coated onto a glass substrate to form a polymer thin film, UV absorption peaks and photoluminescence (PL) spectra were measured. UV maximum absorption peaks of Oxa-PPV, DMOP-PPV, and Oxa-PPV-co-DMOP-PPV were generally found at 441, 303 nm, 454 nm and 570 nm, respectively, depending on the composition ratio. When the 1,3,4-oxadiazole substituent with high electron affinity is introduced, a characteristic peak of 1,3,4-oxadiazole is shown at about 303 nm, but the peak at 303 nm also decreases as the content of oxadiazole in the copolymer decreases. It can be seen. The PL spectrum was measured by using the maximum absorption wavelength of each of the light emitting polymers as the excitation wavelength. In the case of Oxa-PPV, the maximum PL peak and the shoulder at 542 nm were observed at 573 mn, and DMOP-PPV at the maximum PL peak at 539 nm and 520 nm. shoulder was measured. It was found that the Oxa-PPV-co-DMOP-PPV copolymer shifted to a longer wavelength than the maximum emission peak of DMOP-PPV alone as the content of Oxa-PPV increased. In addition, the luminescence phenomenon generated by the 1,3,4-oxadiazole substituent in the PL spectrum was not observed, and thus, it can be seen that an effective energy transfer occurs from the 1,3,4-oxadiazole substituent to the PPV light emitting polymer skeleton.
[110] Example 15. Fabrication of Electroluminescent Device
[111] An electroluminescent device was manufactured using the light emitting polymers Oxa-PPV and DMOP-PPV prepared in Examples 10, 11 and 12 and Oxa-PPV-co-DMOP-PPV which is a copolymerized light emitting polymer. The structure of the fabricated electroluminescent device is shown in FIG. The manufacturing process of the electroluminescent device is to clean the transparent electrode substrate coated with ITO (indium-tin oxide) on the glass substrate, and then ITO glass using a photoresist and an etchant using a microfabrication process The electrode was formed and then washed again. The driving voltage and the luminous efficiency are greatly influenced by the uniformity of the surface of the ITO, the adhesion ability between the electrode and the light emitting polymer interface, and the balance of the carriers (holes and electrons). To solve this problem, PEDOT, a conductive polythiophene derivative, was coated with a thickness of about 100 μs as a hole injection layer and baked at 110 ° C. for about 10 minutes. The light emitting polymer solution prepared by dissolving in chlorobenzene was spin coated on the hole injection layer, and after baking, the solvent was completely removed in a vacuum oven to form a polymer thin film. The polymer solution was spin coated by filtering with a 0.2 μm filter, and the polymer thin film thickness can be freely controlled by adjusting the concentration and spin rate of the polymer solution. The light emitting polymer thickness is about 80-200 nm. In addition, Al, a cathode electrode capable of injecting electrons, was deposited by using a vacuum vaporizer (thermoevaporator) while maintaining a vacuum degree of 4 × 10 −6 torr or less. During deposition, the film thickness and growth rate were controlled by using a crystal sensor. The emission area was 4 ㎜ and the driving voltage was a direct bias voltage.
[112] Example 16. Electroluminescence (EL) Spectrum Measurement and Electro-optical Characterization
[113] The electroluminescent properties of the polymer electroluminescent diode fabricated in Example 15 were evaluated. The monolayer electroluminescent devices of the fabricated ITO / PEDOT / Polymer / Al structure showed typical diode characteristics. In the case of Oxa-PPV, DMOP-PPV and copolymerized light-emitting polymer, Oxa-PPV-co-DMOP-PPV, the driving voltage started at about 4-10 V (Fig. 7) and the amount of carriers injected increased as the voltage increased. As a result, the current density also increased exponentially. The driving voltage of DMOP-PPV is lower than that of Oxa-PPV because the DMOP-PPV is smaller than the HOMO energy level of Oxa-PPV at the HOMO energy level of each light emitting polymer. Because it is easy. In the copolymer, Oxa-PPV-co-DMOP-PPV, the HOMO energy level of the copolymer is similar to that of Oxa-PPV. Oxa-PPV has a role of significantly increasing the LUMO energy level by introducing 1,3,4-oxadiazole substituent which has excellent electron affinity. Accordingly, as the 1,3,4-oxadiazole content was increased in the luminescent polymer energy level diagram of FIG. 5, the LUMO energy levels of the copolymers Oxa-PPV-co-DMOP-PPV and Oxa-PPV increased significantly. It can be seen from FIG. 8 that the injection of electrons from the cathode occurs easily and thus the balance between injected holes and electrons is achieved, resulting in a rapid increase in luminous efficiency. 9 shows the intensity of light emission luminance with respect to an applied voltage. The maximum luminous efficiency and luminous luminance are about 21.1 cd / A and 19500 cd / m2.
[114] Example 17. Comparative Example with MEH-PPV
[115] The following comparative example compared the electro-optical characteristics when using MEH-PPV. FIG. 10 shows the emission spectrum (EL) measured with the voltage fixed at 10 V and emits light in the red region. 11 is a diagram showing a correlation between current and voltage when MEH-PPV is used as a light emitting layer. It can be seen that the current gradually flows at about 3 V in the driving voltage.

权利要求:
Claims (11)
[1" claim-type="Currently amended] The present invention provides a light emitting polymer in which a 1,3,4-oxadiazole derivative or an alkoxyphenyloxy substituent is introduced into the skeleton of a poly (p-phenylenevinylene) light emitting polymer.
[2" claim-type="Currently amended] A light-emitting polymer obtained by copolymerizing a monomer having 1,3,4-oxadiazole of the light-emitting polymer of claim 1 and a monomer having alkoxyphenyloxy substituent introduced therein at various molar compositions.
[3" claim-type="Currently amended] Polymer electroluminescent diodes employed as light emitting materials of claims 1 and 2
[4" claim-type="Currently amended] Luminescent polymer is purified by membrane tube with high purity
[5" claim-type="Currently amended] Side linking sequence of the light emitting polymer of claim 1 is a structure in which a hetero-atom, a 1,4-phenylene ring, and a 1,3,4-oxadiazole and alkoxyphenyloxy ring are connected to a poly (p-phenylenevinylene) skeleton
[6" claim-type="Currently amended] Hetero-atom of claim 5 is a structure that is connected by oxygen, sulfur, nitrogen, silicon, germanium, carbon-carbon triple bond
[7" claim-type="Currently amended] In the alkoxy group of claim 1, aliphatic alkoxy (R1) or branched alkoxy (R2) is introduced, R1 is (CH2) nCH3, R2 is CH2 (CH2) aCH (CH2) bCH3CH (CH3) 2 and a is 0-5, b is an integer from 0 to 10, n is from 0 to 12
[8" claim-type="Currently amended] The molar composition ratio of the 1,3,4-oxadiazole-based light emitting polymer of claim 2 is an integer of 0.9-0.1
[9" claim-type="Currently amended] The light-emitting polymer of Claims 1 and 2 has a weight average molecular weight distribution (Mw) of about 10,000 to 600,000
[10" claim-type="Currently amended] The material of the light emitting layer is characterized by the light emitting polymer derivative used in Claims 1 and 2, and includes anode / light emitting layer / cathode, anode / buffer layer / light emitting layer / cathode, anode / buffer layer / hole transporting layer / light emitting layer / cathode, anode / buffer layer Polymer electroluminescent diode consisting of / hole transport layer / light emitting layer / electron injection layer / cathode
[11" claim-type="Currently amended] Polymer electroluminescent diode using polyline thiophene and polyaniline derivatives which are conductive polymers as buffer layers

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同族专利:

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公开号 | 公开日

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KR100510094B1|2005-08-24|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-09-12|Application filed by 진성호

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2002-09-12|Priority to KR10-2002-0055266A

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2002-10-04|Publication of KR20020075356A

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2005-08-24|Application granted

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2005-08-24|Publication of KR100510094B1

优先权:

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申请号 | 申请日 | 专利标题

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KR10-2002-0055266A|KR100510094B1|2002-09-12|2002-09-12|Highly Efficient Poly Derivatives Containing 1,3,4-Oxadiazole Side Group For Polymer Light Emitting Diodes|