TWI659071B - Coumarin-based green dye contains side chain vinyl triphenylamine - Google Patents

Abstract

The present invention relates to a coumarin-based green dye containing a triphenylamine ethylene side chain, the green dye having a structure represented by the formula (I), wherein R1, R2 and R3 are independently represented by hydrogen, C1-C8 substitution Or an unsubstituted alkyl, alkoxy or halogen. The photophysical property test showed that the molecule represented by the formula (I) has a high fluorescence quantum yield and has a good application potential in the green light conversion film material. The material has strong luminescence, is insensitive to the preparation process, and has stable emission spectra in a large concentration range and temperature range.

Description

Coumarin-based green dye containing triphenylamine ethylene side chain

The invention relates to a novel organic color conversion film material for flat display, in particular to a kind of coumarin-based green light dye containing triphenylamine ethylene side chain, which is formed into a film by solution spin coating, and can be applied to a flat display.

With the continuous breakthrough of the display industry technology and the increasing market demand, flat panel displays have rapidly emerged as a series of display technologies in the 21st century due to their small size, light weight, low power consumption, low radiation, and good electromagnetic compatibility. Mainstream. The coloring method of flat panel display plays a very important role in its production process. Its quality directly determines the color rendering effect, production cost and service life of flat panel display.

At present, the mainstream technology for realizing color display of flat panel display is to print red, green and blue phosphorescent material preparation devices. However, due to the large difference in lifetime and attenuation of the three primary color fluorescent materials, it is easy to cause color cast of color displays. Moreover, the manufacturing process of the three primary color devices is relatively complicated and the cost is high. In order to solve these problems, people have proposed a new idea of color conversion, namely "blue source into color". The "Blue Source Color" technology uses a blue phosphor with a single high brightness as the backlight. The blue light emitted by the backlight is converted into red and green light through the color conversion film, thereby realizing RGB full color display. This technology not only greatly simplifies the production process of electroluminescent flat panel display, improves the color stability and uniformity of the display, but also significantly reduces the production cost of the display. Materials for color conversion films can be classified into inorganic and organic materials. It has been found that, compared with inorganic phosphors, organic conversion materials not only have higher color conversion efficiency, but also have more saturated colors, so that a wider color gamut can be realized, and raw materials are cheaper and easier to obtain, and molecular cutting is easier. Modification for better display.

In the 1990s, the Leising team used the coumarin dye Coumarin 102 as the green light material, and Lumogen F300 used the red dye to disperse in the PMMA to prepare a green and red light conversion film, which achieved a red light conversion efficiency of more than 10%. References: Adv. Mater. , 1997, 9 (1), 33-36). In recent years, domestic research teams have also reported the preparation of organic light conversion films (References: Optoelectronics Letters , 2010, 6 (4), 245-248, CN105267059 A, CN103647003 A), which have obtained a wide color gamut and a light conversion rate. High organic light conversion film. However, these traditional dye molecules are very sensitive to the processing technology, and the color of the luminescence will change greatly after processing at different temperatures or exposure (Reference: Abstract, 2354, 218th ECS Meeting ), so the development of environmentally stable light conversion materials is very necessary.

The organic fluorescent color conversion film generally disperses organic fluorescent dyes having different colors in a solid polymer film by ultraviolet curing or thermal curing, and then excites the organic fluorescent color conversion with a high-brightness blue backlight. The dye molecules in the film realize the color transition, and the converted red, green and background blue light form three primary colors of light, and finally the full color display of the electroluminescent element can be realized.

The present invention provides a coumarin-based green light dye molecule having a triphenylamine ethylene side chain, which is dispersed in a polymer resin such as methyl methacrylate (PMMA) to prepare a light conversion film. . The material has strong luminescence, is insensitive to the preparation process, and has stable emission spectra in a large concentration range and temperature range. a coumarin-based green light dye containing a triphenylamine ethylene side chain, the molecular structure of which is as described in the formula (I), (I)

Wherein R1, R2 and R3 are independently represented by hydrogen, substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen.

Preferably, wherein R1, R2 and R3 are independently represented by hydrogen, substituted or unsubstituted C1-C4 alkyl or alkoxy.

Preferably, wherein R1 and R2 are independently represented by hydrogen, a C1-C4 alkoxy group, and R3 is independently represented by a substituted or unsubstituted C1-C4 alkyl group.

Preferably, R1 and R2 are the same.

Preferably, wherein R1 and R2 are preferably represented by hydrogen or methoxy, and R3 is independently represented by methyl.

The compound of the formula (I) is preferably a compound having the following structure:

The preparation method of the above green dye is prepared by the Heck coupling reaction using the formula A and the formula B: . AB

The preparation method of the formula A is obtained by using C bromination in the following formula, and the reaction formula is as follows: CA.

The preparation method of the formula B is prepared by reacting the following formula D with potassium vinyl fluoroborate under weak alkaline conditions, and the catalyst is tetrakistriphenylphosphine palladium, and the reaction formula is as follows: DB.

The light conversion film is composed of the above green light dye and a cured polymer resin.

The cured polymer resin is an acrylate, an epoxy resin or a polyurethane.

The light conversion film has a total thickness of from 1 to 100 μm.

The use of the above green dye in a light conversion film.

The application is that the green light dye and the cured polymer resin are dissolved in toluene, then spin-coated into a film, dried and solidified to prepare an organic light conversion film, which is fixed on a backlight and applied to a flat display to realize Full color display.

The curing preparation method of the light conversion film may be heat curing or ultraviolet curing.

The backlight is a blue light source, and the cured polymer resin is a methyl methacrylate (PMMA) polymer resin.

The blue light source is a liquid crystal panel, an OLED or an inorganic LED light source.

The molecule represented by the formula (1) has a high fluorescence quantum yield and has a good application potential in the green light conversion film material. The material has strong luminescence, is insensitive to the preparation process, and has stable emission spectra in a large concentration range and temperature range.

In order to describe the present invention in more detail, the following examples are given, but are not limited thereto. CA. DB.

The dye molecules are all prepared by Heck coupling reaction: AB

Example 1 Synthesis of green dye GT1: The synthetic route is shown in Fig. 1.

(1) Synthesis of Compound 2a Synthesis step: To a 250 mL reaction flask was added compound 1a (6.48 g, 20 mmol) (commercially available), potassium fluoroborate (3.22 g, 24 mmol), tetratriphenylphosphine palladium (8.3 g, 5%) , K ₂ CO ₃ (6.48 g, 60 mmol), toluene (70 mL) and water (14 mL). The nitrogen gas was evacuated 3 times, heated to 80 ° C, and maintained at this temperature for 8 hours. The reaction of Compound 1a was completely confirmed by TLC. After the reaction, the heating was stopped, the temperature was lowered to 20 ° C, and the reaction mixture was poured into water, and then extracted with EA (100 mL*3). The crude column chromatography gave white compound 2a (4 g, yield 73.7%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 5.15 (d, J = 10.88 Hz, 1 H) 5.63 (d, J = 17.61 Hz, 1 H) 6.66 (dd, J=17.48, 10.88 Hz, 1 H) 6.92 - 7.05 (m, 4 H) 7.09 (d, J=8.19 Hz, 4 H) 7.19 - 7.38 (m, 6 H).

(2) Synthesis of Compound 4a Synthesis step: Compound 3a (7 g, 30 mmol) (commercially available), NBS (5.9 g, 39 mmol) and chloroform (50 mL) were added to a 250 mL reaction flask. The reaction was carried out for 2 hours at room temperature, and the compound 3a was completely reacted by TLC. Post-reaction treatment: The reaction was stopped, and the reaction mixture was poured into water, dichloromethane (100 mL*2) was evaporated and evaporated. The crude column chromatography gave pale yellow compound 4a (5 g, yield 53.7%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 1.21 (t, J=7.09 Hz, 6 H) 2.45 - 2.62 (m, 3 H) 3.32 - 3.50 (m, 4 H) 6.49 (d, J=2.57 Hz , 1 H) 6.60 (dd, J=9.05, 2.57 Hz, 1 H) 7.43 (d, J=9.05 Hz, 1 H).

(3) Synthesis of GT1 Synthesis step: Compound 4a (0.31 g, 1 mmol), compound 2a (0.352 g, 1.3 mmol) Pd ₂ (dba) ₃ (15 mg, 5%), tri-tert-butylphosphine (30) was added to a 250 mL reaction flask. Mg, 10%), triethylamine (0.6 mL) and DMF (5 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 100 ° C by heating. The temperature was maintained for 12 hours, and the compound 4a was completely reacted by TLC. After the reaction, the heating was stopped, the temperature was lowered to 20 ° C, and the reaction mixture was poured into water, and ethyl acetate (50 mL*2) was evaporated. The crude column chromatography gave the pale yellow compound GT1 (0.15 g, yield 30%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 1.22 (t, J=7.03 Hz, 7 H) 2.50 (s, 3 H) 3.42 (q, J=7.05 Hz, 4 H) 6.51 (s, 1 H) 6.61 (d, J=9.17 Hz, 1 H) 6.97 - 7.07 (m, 6 H) 7.11 (d, J=7.95 Hz, 4 H) 7.23 (br. s., 2 H) 7.27 (s, 1 H) 7.40 (d, J=8.31 Hz, 2 H) 7.47 (d, J=8.93 Hz, 1 H) 7.56 (d, J=16.14 Hz, 1 H).

Example 2 Synthesis of green dye GT2: The synthetic route is shown in Fig. 2.

(1) Synthesis of Compound 3b Synthesis step: To a 250 mL reaction flask was added compound 1b (4.58 g, 20 mmol) (commercially available), compound 2b (commercially available) (8.5 g, 30 mmol), Pd ₂ (dba) ₃ (920 mg, 5%) ), tri-tert-butylphosphine (400 mg, 10%), sodium tert-butoxide (4.58 g, 40 mmol) and toluene (100 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 110 ° C by heating. The temperature was maintained for 12 hours, and the reaction of Compound 1b was completely confirmed by TLC. After the reaction, the heating was stopped, and the mixture was cooled to 20 ° C. The reaction mixture was poured into water, and ethyl acetate (10 mL*2) was evaporated. The crude product was purified by column chromatography to afford pale yellow compound 3b (4.3 g, yield 56.4%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 3.79 (s, 6 H) 6.67 - 6.88 (m, 6 H) 7.02 (d, J=8.93 Hz, 4 H) 7.23 (d, J=8.80 Hz, 2 H).

(2) Synthesis of Compound 4b Synthesis step: To a 250 mL reaction flask was added compound 3b (4 g, 10.4 mmol), potassium fluoroborate (1.67 g, 12.5 mmol), tetratriphenylphosphine palladium (580 mg, 5%), K ₂ CO ₃ (3.24 g, 30 mmol), toluene (100 mL) and water (20 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 80 ° C by heating. The temperature was maintained for 8 hours, and the compound 3b was completely reacted by TLC. After the reaction, the heating was stopped, the temperature was lowered to 20 ° C, and the reaction mixture was poured into water, and then extracted with EA (100 mL*3). Crude column chromatography gave white compound 4b (2.8 g, yield: 81.2%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 3.79 (s, 6 H) 5.09 (d, J = 10.88 Hz, 1 H) 5.58 (d, J = 17.61 Hz, 1 H) 6.51 - 6.70 (m, 1 H) 6.73 - 6.84 (m, 5 H) 6.87 (d, J=8.56 Hz, 1 H) 6.95 - 7.09 (m, 4 H) 7.14 - 7.25 (m, 2 H).

(3) Synthesis of GT2 Synthesis step: To a 250 mL reaction flask was added compound 4b (1 g, 3.2 mmol) (commercially available), compound 4a (1.42 g, 4.2 mmol) Pd ₂ (dba) ₃ (50 mg, 5%), tri-tert-butyl Phosphine (200 mg, 10%), triethylamine (5 mL) and DMF (10 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 100 ° C by heating. The temperature was maintained for 12 hours, and the compound 4a was completely reacted by TLC. After the reaction, the heating was stopped, the temperature was lowered to 20 ° C, and the reaction mixture was poured into water, and ethyl acetate (50 mL*2) was evaporated. The crude column chromatography gave the pale yellow compound GT2 (0.55 g, yield 30.7%). ¹ H NMR (400 MHz, CHLOROFORM-d) ppm 1.21 (t, J=7.03 Hz, 6 H) 2.49 (s, 3 H) 3.42 (q, J=7.01 Hz, 4 H) 3.80 (s, 6 H) 6.50 (d, J=2.45 Hz, 1 H) 6.61 (dd, J=8.93, 2.32 Hz, 1 H) 6.83 (d, J=8.93 Hz, 4 H) 6.90 (d, J=8.56 Hz, 2 H) 7.00 (d, J=16.26 Hz, 1 H) 7.06 (d, J=8.93 Hz, 4 H) 7.34 (d, J=8.68 Hz, 2 H) 7.46 (d, J=9.05 Hz, 1 H) 7.49 - 7.57 (m, 1 H).

Example 3 Photophysical properties of green dyes GT1 and GT2: The photophysical properties of green dyes GT1 and GT2 in solution were determined by dissolving the corresponding dye in toluene or dichloromethane at a concentration of 1 x 10 ^{- The 5} mol/L dye-based CCF film is prepared by dissolving the dye and the corresponding proportion of PMMA in toluene, spin coating and drying. The photophysical properties of the dye film are determined by dissolving the dye in THF and then spin coating to prepare the film. . The CCF film prepared with GT1 and GT2 has good absorption of background blue light (λ _max ≈450 nm). See Fig. 3 and Fig. 5, the emitted light is green light, see Fig. 4 and Fig. 6. GT1 and GT2 have strong luminescence (quantum yield EQE close to 70%), are not sensitive to the preparation process, and their emission spectra are stable over a large concentration and temperature range. Figure 7 is the fluorescence emission spectrum of the classic green dye C545T mixed in PMMA to form a light conversion film. It can be seen that small changes in the proportion of the impurities will cause a large change in the luminescence spectrum, and its luminescence is stable. The result is very poor. Fig. 8 is a fluorescent emission light of a light conversion film prepared by the green dye GT2 of the present invention, and it can be seen that it is dispersed in PMMA at different concentrations, and its spectrum is very stable.

1 is a schematic view showing the synthesis route of the green light dye GT1 of the present invention; FIG. 2 is a schematic view showing the synthesis route of the green light dye GT2 of the present invention; FIG. 3 is a blue light dye GT1 of the present invention in toluene, dichloromethane and UV-visible absorption spectrum of PMMA film and solid state; Figure 4 is a fluorescence emission spectrum of green light dye GT1 of the present invention in toluene, dichloromethane and PMMA film and solid state; Figure 5 is the green light of the present invention UV-visible absorption spectrum of dye GT2 in toluene, dichloromethane and PMMA film and solid state; Figure 6 is a fluorescence emission spectrum of green light dye GT2 of the present invention in toluene, dichloromethane and PMMA film and solid state; 7 is a fluorescence emission spectrum of a classic green light dye C545T doped with a light conversion film film in PMMA at different ratios; and FIG. 8 is a fluorescence emission of a light conversion film prepared by the green light dye GT2 of the present invention. spectrum.

Claims (10)

A coumarin-based green light dye containing a triphenylamine ethylene side chain, the molecular structure of which is as described in formula (I): Wherein R1, R2 and R3 are independently represented by hydrogen, substituted or unsubstituted C1-C8 alkyl, C1-C8 alkoxy or halogen. The green dye according to claim 1, wherein R1, R2 and R3 are independently represented by hydrogen, a substituted or unsubstituted C1-C4 alkyl group, or a C1-C4 alkoxy group. The green dye according to claim 2, wherein R1 and R2 are independently represented by hydrogen, a C1-C4 alkoxy group, and R3 is independently represented by a substituted or unsubstituted C1-C4 alkyl group. The green dye according to claim 3, wherein R1 and R2 are the same. The green dye according to claim 4, wherein R1 and R2 are represented by hydrogen, a C1-C4 alkoxy group, and R3 is independently represented by a C1-C4 alkyl group. The green light dye as described in claim 5 of the patent application has the following structural formula: A method for preparing a green dye according to any one of claims 1 to 6, which is prepared by a Heck coupling reaction using Formula A and Formula B: The method of claim 7, wherein the preparation method of the formula A is obtained by using C bromination in the following formula, and the reaction formula is as follows: The method of claim 7, wherein the preparation method of the formula B is prepared by reacting D with potassium vinyl fluoroborate in a weak basic condition under mild alkaline conditions, and the catalyst is tetratriphenylbenzene. Phosphine palladium, the reaction formula is as follows: The green dye according to any one of claims 1 to 6, which is used in a light conversion film.