CN102093232B - Trifluorenamine compound, trifluorenamine polymer luminescent material, preparation method and application - Google Patents

Abstract

The invention discloses a tri-fluoreneamine compound, a tri-fluoreneamine polymer luminescent material, a preparation method and application thereof, wherein tri-fluoreneamine is taken as a framework, and the bipolar and luminescent color of the luminescent material can be regulated and controlled by changing the chemical structure of the side chain of the tri-fluoreneamine-containing polymer luminescent material; the preparation method is characterized in that fluorene is used as an initial reaction raw material, a series of simple reactions are carried out, and finally, Suzuki coupling reaction catalyzed by palladium and diboronic ester of fluorene are subjected to alternating copolymerization to obtain the target polymer luminescent material. The material is simple to synthesize and convenient to purify; the film has better solubility, film forming property and film form stability; has high photoluminescence and electroluminescence efficiency. The material is applied to a light-emitting layer of a polymer electroluminescent diode.

Description

Trifluorenamine compound, trifluorenamine polymer luminescent material, preparation method and application

technical field

The invention relates to a light-emitting conjugated polymer material, in particular to a polymer light-emitting material with trifluorenamine as a skeleton, a preparation method thereof, and an application of the material in a polymer light-emitting diode.

Background technique

Since Burroughes and Friend first reported polymer light-emitting diodes (PLEDs), in the past nearly two decades, PLEDs have aroused intense research and development interest in fabricating ultra-thin, full-color, and large-area flat-panel displays. made great progress. The solution processability of PLEDs allows people to prepare devices by low-cost printing techniques, such as inkjet printing and screen printing, which are lower in cost than vacuum-evaporated small-molecule organic light-emitting diodes. is also more feasible. In order to realize PLEDs-based flat-panel displays and solid-state lighting, high-performance red, green, and blue light-emitting polymers are required. Among them, the blue-light polymer can be used not only as the light-emitting layer, but also as the host material of the light-emitting guest, and obtain long-wavelength light through energy transfer or carrier capture. The most representative of the existing polymer blue light-emitting materials is polyfluorene, but because of the rigid planar structure of fluorene, the material is easy to form an excimer complex and emit long-wavelength light, which seriously affects the saturated color of the light emitted by the device. Purity and stability of luminous color. At the same time, polyfluorene has a higher hole injection barrier due to its lower lowest occupied molecular orbital (HOMO) energy level.

Contents of the invention

The object of the present invention is to provide a polymer luminescent material and a preparation method thereof in view of the existing technical shortcomings. The material has the advantages of high quantum efficiency, good color purity, and good long-term stability, and is suitable for high-resolution full-color display and white light illumination.

The purpose of the present invention is also to provide a polymer containing trifluoreneamine for preparing the above-mentioned luminescent material and a preparation method thereof.

Another object of the present invention is to apply the polymer electroluminescent material containing trifluorenamine to the preparation of polymer light-emitting diodes and lighting devices.

The object of the present invention is achieved through the following technical solutions:

A trifluorene amine compound, the compound has the following chemical structure:

Wherein: R ₁ is a solubilizing alkyl or alkoxy group with 1 to 20 carbon atoms; X is a functional group, a heterocyclic compound or a derivative of carbazole.

Preferably, the structure of X is as follows:

Preferably, said Ar has the following structure:

The preparation method of above-mentioned trifluorene amine compound, comprises the steps:

Under argon atmosphere, add 2-amino-9,9-dioctylfluorene inducer and 2 , 7-dibromo-9,9-dioctylfluorene, and dissolved in toluene, then add Pd ₂ (dba) equivalent to 1/40 of the molar weight of 2-amino-9,9-dioctylfluorene inducer ₃ , 1/10 of DPPF and 10 times of ^tBuONa , react under heating and reflux for 24 to 36 hours, cool naturally after the reaction, extract with ethyl acetate, and wash with saturated brine, the obtained organic layer is washed with anhydrous sulfuric acid Magnesium drying, suction filtration, the resulting filtrate removes the solvent under reduced pressure, separates through a chromatographic column, evaporates the solvent and vacuum-dries to obtain a trifluorene amine compound.

The trifluorenamine polymer luminescent material prepared from the above trifluorenamine compound has the following chemical structure:

Luminescent material I

or

Luminescent material II

Wherein: R ₁ is a solubilizing alkyl or alkoxy group, and the number of carbon atoms is 1 to 20; R ₂ is a variety of substituent groups; X is a functional group, a heterocyclic compound and a derivative of carbazole; y+z< 1, and 0<y<1, 0≤z<1, n=10-1000.

Preferably, when 0.01≤y<0.5, z=0.1, R ₂ is H; when y=0.5, z=0, R ₂ is H.

The preparation method of above-mentioned luminescent material I, comprises the steps:

The polymer was prepared by Suzuki coupling reaction, and 2,7-bisboronic acid esters of 9,9-dialkylfluorene, equivalent molar amounts of the bisboronic acid esters were added to the reaction flask under nitrogen or argon atmosphere. The trifluorene amine compound is dissolved in toluene equivalent to 30 to 150 times the total molar amount of the above two reactants, and then an aqueous solution of tetraethylammonium hydroxide equivalent to 1 to 10 times the total molar amount of the above two reactants and 1% to 10% catalyst, heated and refluxed and stirred for 12 to 48 hours; after natural cooling, the end-capping reaction was carried out; after the reaction was completed, natural cooling was used to precipitate the polymer with methanol, and the dried product was washed with methanol and acetone respectively. and tetrahydrofuran extraction for 24 hours, the extract was concentrated, precipitated in methanol, and the final product was dried under vacuum to obtain luminescent material I.

The difference between the preparation method of the above-mentioned luminescent material II and the luminescent material I is:

Also add 2,7-dibromo-9,9-dioctylfluorene reactant in Suzuki coupling reaction system; When adding y part of trifluorene amine compound, 0＜y≤0.5, then add 0.5 part (mol fraction, The same below) 2,7-diboronic acid ester of 9,9-dialkylfluorene and (0.5-y) parts of 2,7-dibromo-9,9-dioctylfluorene, at this time z=0; or

Dibromodibenzothiophene-S, S-dioxygen and 2,7-dibromo-9,9-dioctylfluorene are also added to the Suzuki coupling reaction system; when adding y parts of trifluorenamine Compound, 0<y<0.5, z parts of dibromodibenzothiophene-S, S-dioxygen, 0<z<0.5, y+z≤0.5, then add 0.5 parts of 9,9-dialkylfluorene of 2 , 7-bisboronate and (0.5-y-z) parts of 2,7-dibromo-9,9-dioctylfluorene.

Preferably, the catalyst is one or a mixture of tetrakis(triphenylphosphine)palladium, palladium acetate and tricyclohexylphosphine.

The luminescent material is used as a hole transport layer material in the luminescent layer of a polymer electroluminescent diode.

The present invention introduces trifluorenamine into the main chain of the polymer to increase the HOMO energy level of the polymer and improve the hole injection characteristics while improving the three-dimensional structure of the polymer to avoid the formation of exciplexes, thereby inhibiting the resulting Long-wave emission to improve the saturation color purity of emitted light and the stability of luminous color. In addition, by introducing various groups on the fluorene as the side chain of the polymer, the electron affinity of the entire molecule is regulated, so that the prepared polymer light-emitting material has certain bipolar properties. By adjusting the bipolarity of the polymer, the balance of charge carrier (electron and hole) injection and transport in the polymer light-emitting layer can be better achieved, so that the polymer prepared by the solution processing method of spin coating can be electroluminescent Diodes have better device performance. At the same time, by introducing different chromophoric groups at this position, the purpose of regulating the luminous color of the polymer luminescent material can also be achieved. During the preparation, cheap fluorene was used as the initial reaction raw material, through a series of simple reactions, and finally the target polymer light-emitting material was obtained by palladium-catalyzed Suzuki coupling reaction and bis-boronate copolymerization of fluorene; in addition, by introducing two Bromodibenzothiophene-S, S-dioxygen, by random copolymerization, has obtained a blue light material with relatively excellent performance. This series of conjugated polymer light-emitting materials, as the light-emitting layer material for making polymer electroluminescent diodes, has very broad development and application prospects in large-area flat-panel full-color display screens, background light sources for liquid crystal displays, and white light lighting sources. Therefore, compared with existing materials and technologies, the present invention has the following advantages and beneficial effects:

(1) The polymer luminescent material containing trifluorene amine is easy to synthesize and easy to purify;

(2) The polymer luminescent material containing trifluorene amine has good solubility, film-forming property and film shape stability;

(3) The trifluorenamine-containing polymer luminescent material has a higher HOMO energy level and a lower hole injection barrier;

(4) By changing the chemical structure of the side chain of the trifluorenamine-containing polymer luminescent material, the bipolarity and luminescent color of the luminescent material can be adjusted;

(5) The trifluorenamine-containing polymer luminescent material has high photoluminescence and electroluminescence efficiencies.

Description of drawings

Fig. 1 is the ultraviolet-visible absorption spectrum of the polymer prepared in Examples 1-4 in toluene solution.

Fig. 2 is the fluorescence spectrum of the polymer prepared in Examples 1-4 in toluene solution.

Fig. 3 is the ultraviolet-visible absorption spectrum of the polymer prepared in Examples 1-4 in the solid film state.

Fig. 4 is the fluorescence spectrum of the polymer prepared in Examples 1-4 in the state of solid film.

Fig. 5 is the electroluminescent spectrum of the polymers prepared in Examples 1-4 in the solid film state.

Fig. 6 is the electroluminescent spectrum (with TPBI layer added) of the polymer prepared in Examples 1-4 in the state of solid thin film.

Fig. 7 is the ultraviolet-visible absorption spectrum of the polymer prepared in Examples 5-13 in toluene solution.

Fig. 8 is the fluorescence spectrum of the polymers prepared in Examples 5-13 in toluene solution.

Fig. 9 is the ultraviolet-visible absorption spectrum of the polymers prepared in Examples 5-13 in the state of solid film.

Fig. 10 is the fluorescence spectrum of the polymers prepared in Examples 5-13 in the state of solid film.

Fig. 11 is an electroluminescent spectrum diagram of the polymers of Examples 10-13 in a solid thin film state.

Fig. 12 is an electroluminescent spectrum diagram (with TPBI layer added) of the polymers of Examples 10-13 in a solid thin film state.

Detailed ways

The present invention will be described in further detail below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto.

Example 1

Step 1: Preparation of 2-nitrofluorene

Fluorene (33.2g, 0.2mol) was dissolved in 200ml glacial acetic acid, stirred, heated to about 60°C, and concentrated HNO ₃ (32ml, 0.464mol) diluted with 15ml glacial acetic acid was added dropwise through a constant pressure dropping funnel. After the dropwise addition was completed, the reaction was carried out at 60° C. for 3 hours. The reaction mixture was poured into ice water, extracted with dichloromethane, the obtained organic layer was washed 3 times with saturated saline solution, and the organic phases were combined and dried over anhydrous magnesium sulfate. The filtrate after suction filtration was desolventized under reduced pressure, and then recrystallized with absolute ethanol to obtain 30.3 g of a khaki solid. Yield 71.6%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.71 (s, 1H), 8.60-8.31 (m, 1H), 7.91-7.88 (m, 2H), 7.66-7.64 (m, 1H), 7.48 -7.46(m, 2H), 4.03(s, 2H).

Step 2: Preparation of 2-nitro-9,9-dioctylfluorene

Under a nitrogen atmosphere, 2-nitrofluorene (5.30 g, 25 mmol) and tetrabutylammonium bromide (0.449 g, 1.25 mmol) were added to a 250 ml three-necked flask, and 100 ml of toluene was added to dissolve them. Add n-octyl bromide (12.8 g, 66.3 mmol) with a dropper, and after about half an hour, add 40 ml of 50% NaOH, and the mixture turns purple-black. React at 60°C for about 8 hours. After natural cooling, the reaction was quenched with a certain amount of hydrochloric acid, and 100 ml of water was added, extracted with ethyl acetate, washed with saturated brine for 3 times, and the obtained organic layer was dried with anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. Column separation, the mobile phase used (pure petroleum ether, then petroleum ether/dichloromethane = 1:6, 1:4) was spin-dried, and vacuum-dried to obtain 10.0 g of light yellow oily liquid with a yield of 91.5%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.30-8.22 (m, 1H), 8.20 (m, 1H), 7.80-7.78 (m, 2H), 7.43-7.38 (m, 3H), 2.05 -1.20(m, 4H), 1.28-1.03(m, 20H), 0.88-0.78(m, 6H), 0.59-0.52(m, 4H).

Step 3: Preparation of 2-amino-9,9-dioctylfluorene

Under an argon atmosphere, add 2-nitro-9,9-dioctylfluorene (4.38 g, 10 mmol) and 50 ml of absolute ethanol into a 50 ml three-neck flask, stir and dissolve. Then 5% Pd/C (1.05 g, 0.5 mmol) was added, and hydrazine monohydrate (2.4 ml) was added dropwise with a needle, and the drop was completed within 20 minutes. The reaction was carried out at 80° C. for 10 hours. After natural cooling, it was filtered to obtain 4.08 g of the product with a yield of 100%.

¹ H NMR (300MHz, DMSO), δ (ppm): 7.50(d, 1H), 7.40(d, 1H), 7.25(d, 1H), 7.19(t, 1H), 7.09(t, 1H), 6.55 (s, 1H), 6.50(d, 1H), 5.19(s, 2H), 1.83(m, 4H), 1.22-0.91(m, 20H), 0.79(t, 6H), 0.51(m, 4H).

Step 4: Preparation of 2-nitro-7-bromo-9,9-dioctylfluorene

Add 5.46g (12.5mmol) 2-nitro-9,9-dioctylfluorene and 0.137g iron powder into a 250ml three-necked flask, then measure 50ml chloroform with a graduated cylinder, pour it into the flask, and place it under ice-salt bath Stir and protect from light. Use a 2ml pipette to pipette 1.3ml (18.8mmol) of liquid bromine, add it to a 100ml constant pressure dropping funnel, and add it dropwise to the flask, while the tail gas generated enters the saturated sodium thiosulfate solution through the catheter. React for 9 hours, quench the reaction with saturated sodium thiosulfate solution, extract with dichloromethane and wash with saturated sodium chloride solution, dry the organic layer with anhydrous magnesium sulfate, spin dry after suction filtration, and perform column layer Analysis (petroleum ether/CH ₂ Cl ₂ 3:1), and vacuum drying gave 5.42 g of light yellow solid, which was identified by ¹ HNMR. The yield was 84.0%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.28-8.24 (m, 1H), 8.19-8.18 (m, 1H), 7.75-7.63 (m, 2H), 7.55-7.52 (m, 2H) , 2.08-1.92(m, 4H), 1.24-1.04(m, 20H), 0.84-0.79(t, 6H), 0.60-0.51(m, 4H).

Step 5: Preparation of 2,7-dibromofluorene

The method is the same as step 4, only need to change 2-nitro-9,9-dioctylfluorene to fluorene (16.7 g, 0.1 mol), and the product is a light yellow solid. Yield 86.0%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.66 (m, 2H), 7.62 (s, 1H), 7.59 (s, 1H), 7.52 (m, 1H), 7.49-7.49 (m, 1H ), 3.87(s, 2H).

Step 6: Preparation of 2,7-dibromo-9,9-dioctylfluorene

Add dibromofluorene (27.8g, 85.9mmol), 230ml dimethyl sulfoxide, and phase transfer catalyst tetrabutylammonium bromide (0.252g, 0.78mmol) into a 500ml flask, and stir. Add 20ml of 50% NaOH solution, the mixture is purple-black. Stir for 1-2 hours. n-Octyl bromide (35.7 g, 185 mmol) was added dropwise into the constant pressure dropping funnel, and reacted overnight for 18 hours. Add appropriate amount of concentrated hydrochloric acid to neutralize and cool with ice water. Extract with dichloromethane, wash the organic layer three times with concentrated brine, dry over anhydrous magnesium sulfate, and filter with suction, and remove the solvent from the filtrate under reduced pressure to obtain a reddish-brown liquid. Pass through the column with petroleum ether as the mobile phase, and recrystallize with ethanol as the solvent to obtain 39.2 g of a colorless solid. Yield 83.2%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.50 (m, 1H), 7.49-7.48 (m, 1H), 7.46-7.46 (m, 1H), 7.44-7.38 (m, 3H), 1.93 -1.88(m, 4H), 1.25-1.05(m, 20H), 0.85-0.80(t, 6H), 0.58-0.56(m, 4H).

Step 7: Preparation of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-)-9,9-dioctylfluorene

Under Ar atmosphere, 2,7-dibromo-9,9-dioctylfluorene (20.1 mmol, 11.0 g) was added into a 250 ml three-neck flask and sealed. After about 30 minutes, add 170 ml of freshly distilled THF with a needle to fully dissolve 2,7-dibromo-9,9-dioctylfluorene, and stir for 20 minutes. After cooling to -78°C with liquid nitrogen, add n-butyllithium (50mmol, 20ml) dropwise with a needle, the reaction solution turns orange-yellow, and then colorless. Stir at -78°C for 2.5 hours, the mixture is milky white , the temperature rose to -40°C, added liquid nitrogen to cool down to -78°C, quickly added borate (10.5ml, 50mmol) with a needle, the solution turned orange, stirred, the mixture gradually warmed up, and finally became milky white, overnight . React for 18 hours. Add an appropriate amount of water, stir, and quench the reaction. The color of the mixture becomes clear. Extraction is performed with dichloromethane. The lower colorless oil layer is removed and washed three times with concentrated brine. The obtained organic layers were combined, dried over anhydrous magnesium sulfate, and filtered with suction to obtain a colorless filtrate. The solvent was removed under reduced pressure to obtain a colorless solid. Recrystallized once with ethanol and dichloromethane as a mixed solvent to obtain 9.15 g of white solid with a yield of 70.5%.

¹ H NMR (300MHz, CDCl ₃ ), δ(ppm): 7.79(d, 2H), 7.74-7.73(m, 3H), 7.70(s, 1H), 2.00(m, 4H), 1.39(s, 24H ), 1.30-1.01(m, 20H), 0.83-0.78(t, 6H), 0.55(m, 4H)

Step 8: Preparation of bis(7-bromo-9,9-dioctylfluoren-2-)-(9,9-dioctylfluoren-2-)amine

Under an argon atmosphere, into a 50ml three-necked flask, add 2,7-dibromo-9,9-dioctylfluorene (2.23g, 4.77mmol), 2-amino-9,9-dioctylfluorene ( 0.918g, 2.27mmol), dissolved in 20ml of toluene. Further _Pd2 (dba) ₃ (0.576g, 0.0628mmol), DPPF (0.121g, 0.218mmol), ^tBuONa (0.878g, 9.13mmol) were added. The reaction was carried out at 110° C. for 40 hours. After natural cooling, it was extracted with dichloromethane, washed three times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. Column separation, the mobile phase used is pure petroleum ether. After being spin-dried, vacuum-dried to obtain 2.14 g of the product with a yield of 80.0%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.62-7.41 (m, 9H), 7.33-7.27 (m, 4H), 7.24-7.23 (m, 3H), 7.02-6.98 (m, 3H) , 1.96-1.78(m, 12H), 1.25-1.07(m, 60H), 0.87-0.81(t, 18H), 0.67(m, 12H).

Step 9: Preparation of polymer P4FN:

Under an argon atmosphere, add raw material bis(7-bromo-9,9-dioctylfluorene-2-)-(9,9-dioctylfluorene-2-)amine (0.581g , 0.433mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-)-9,9-dioctylfluorene (0.281g, 0.433mmol), Et ₄ NOH 1ml, and diluted with 1ml of deionized water, the catalyst Pd(pph ₃ ) ₄ (0.0065g, 0.00562mmol), after passing through Ar for 30 minutes, the temperature was gradually raised to 90-100°C, and the reaction was carried out for 48 hours. Cool naturally, add phenylboronic acid (0.137g, 1.12mmol), 2ml toluene, and react for 13 hours. After natural cooling, 1ml of bromobenzene (9.6mmol) was added and reacted for 10 hours. The resulting dark blue-green viscous was dissolved with toluene, precipitated with methanol, filtered, and turned into light yellow-green, and dried in vacuo. Then, they were extracted with methanol, acetone and THF for 24 hours respectively. Concentrate, precipitate in methanol, filter and dry in vacuo. Obtained 0.4235g, yield 58.0%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.90-7.80 (m, 2H), 7.79-7.50 (m, 14H), 7.43-7.31 (m, 5H), 7.20-7.03 (m, 3H) , 2.30-1.75(m, 16H), 1.40-1.00(m, 80H), 0.99-0.50(m, 40H).

The absorption spectrum and fluorescence spectrum of the polymer film are shown in Fig. 3 and Fig. 4 .

In order to characterize the electroluminescent properties of the polymer, the device structures were fabricated as ITO/PEDOT:PSS/Polymer(80nm)/CsF(1.5nm)/Al(120nm) and ITO/PEDOT:PSS/Polymer(80nm)/TPBI (30nm)/CsF(1.5nm)/Al(120nm) polymer electroluminescent diode device, the manufacturing process is as follows: use pre-cleaned ITO glass as the anode, spin-coat a layer of conductive polymer-polythiophene on the glass Derivatives (PEDOT:PSS), and vacuum-dried at 80°C for 12 hours, then spin-coated a layer of blue-light conjugated polymer with a thickness of 80nm on the PEDOT:PSS modified layer, and heated at 80°C for 20min. Then evaporate 30nm thick TPBI (compared with non-evaporated TPBI), 1.5nm thick CsF and 120nm thick metal aluminum under high vacuum. Finally, the packaging of the device. The performance of the device is as follows: start-up voltage 3.0V, maximum brightness 747cd/m ² , maximum current efficiency 0.48cd/A, maximum external quantum efficiency 0.59%, color coordinates (CIE) (0.165, 0.123). The performance of the device without TPBI is as follows: start-up voltage 3.1 volts, maximum brightness 257cd/m ² , maximum current efficiency 0.06cd/A, maximum external quantum efficiency 0.07%, color coordinates (CIE) (0.208, 0.218). Its electroluminescent spectrum is shown in Figure 5 and Figure 6.

Example 2

The first seven steps of the present embodiment are the same as the first seven steps of Embodiment 1.

Step 8: Preparation of 2-cyano-7-nitro-9,9-dioctylfluorene

Under an argon atmosphere, 2-nitro-7-bromo-9,9-dioctylfluorene (2.05g, 4mmol), CuCN (0.389g, 4mmol), DMF (30ml) were added to a 250ml three-necked flask, After stirring evenly, gradually raise the temperature to about 150°C, and react under reflux for about 15 hours, showing a light yellow color. Overnight, it was found to be orange-red. It was extracted with dichloromethane, washed three times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. For column separation, the mobile phase used is dichloromethane/petroleum ether=1:6, remove the raw material point, dichloromethane/petroleum ether=1:3, collect the second point. Vacuum drying afforded 1.53 g of a reddish-brown solid. Yield 83.2%.

¹ H NMR (300MHz, CDCl ₃ ), δ(ppm): 8.32(d, 1H), 8.24(s, 1H), 7.89(d, 2H), 7.70(m, 2H), 2.08-2.01(m, 4H ), 1.25-1.06(m, 20H), 0.88-0.80(t, 6H), 0.60-0.38(m, 4H).

Step 9: Preparation of 2-amino-7-cyano-9,9-dioctylfluorene

The method is the same as step three, only need to replace 2-nitro-9,9-dioctyl fluorene with 2-cyano-7-nitro-9,9-dioctyl fluorene (1.13g, 2.2mmol) to obtain orange Yellow viscous body 0.7637g, yield 72.3%.

¹ H NMR (300MHz, DMSO), δ (ppm): 7.64 (s, 1H), 7.55 (s, 2H), 7.53 (d, 1H), 5.53 (s, 2H), 2.00-1.75 (m, 4H) , 1.22-0.99(m, 20H), 0.78(t, 6H), 0.51-0.49(m, 4H).

Step 10: Preparation of bis(7-bromo-9,9-dioctylfluorene-2-)-(7-cyano-9,9-dioctylfluorene-2-)amine

Under argon atmosphere, into a 50ml three-necked flask, add 2,7-dibromo-9,9-dioctylfluorene (2.30g, 4.18mmol), 2-amino-7-cyano-9,9- Dioctylfluorene (0.360 g, 0.837 mmol), dissolved in 20 ml of toluene. Further _Pd2 (dba) ₃ (0.0164 g, 0.021 mmol), DPPF (0.0399 g, 0.0837 mmol), ^tBuONa (0.390 g, 3.48 mmol) were added. The reaction was carried out at 110° C. for 24 hours. After natural cooling, it was extracted with ethyl acetate, washed three times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. For column separation, the mobile phase used was petroleum ether/dichloromethane=1:6, 1:3. After drying in vacuo, 0.900 g of the product brownish-yellow viscous body was obtained, with a yield of 78.8%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.68-7.60 (m, 2H), 7.60-7.50 (m, 6H), 7.50-7.46 (m, 4H), 7.46-7.43 (m, 2H) , 7.07-7.00(m, 4H), 2.07-1.81(m, 12H), 1.27-1.09(m, 60H), 0.89(m, 18H), 0.84-0.69(m, 12H).

Step 11: Preparation of polymer P4FNCN

Under an argon atmosphere, add the raw material bis(7-bromo-9,9-dioctylfluorene-2-)-(7-cyano-9,9-dioctylfluorene-2- )amine (0.755g, 0.55mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-)-9,9-dioctyl Fluorene (0.358g, 0.55mmol), Et ₄ NOH 2ml, and diluted with deionized water 2ml, catalyst Pd(pph ₃ ) ₄ (8.4mg, 0.0073mmol), toluene 10ml. After passing Ar for 30 minutes, the temperature was gradually raised to 90-100° C., and the reaction was carried out for 48 hours. Cool naturally, add phenylboronic acid (11.2mg, 0.0918mmol), toluene 3ml, and react for 12 hours. After natural cooling, 1ml of bromobenzene (9.6mmol) was added and reacted for 12 hours. The viscous material was dissolved with toluene and precipitated with methanol, filtered and dried in vacuo. Then, they were extracted with methanol, acetone and THF for 24 hours respectively. Concentrate, precipitate in methanol, filter and dry in vacuo. Obtained 0.770g, yield 79.6%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.88-7.78 (m, 2H), 7.77-7.52 (m, 15H), 7.37-7.27 (m, 4H), 7.17-7.02 (m, 3H) , 2.30-1.75(m, 16H), 1.40-1.00(m, 80H), 0.99-0.48(m, 40H).

The absorption spectrum and fluorescence spectrum of the polymer film are shown in Fig. 3 and Fig. 4 .

The implementation steps of the device are the same as those in Embodiment 1. The performance of the device is as follows: start-up voltage 3.5V, maximum brightness 1133cd/m ² , maximum current efficiency 1.16cd/A, maximum external quantum efficiency 1.21%, color coordinates (CIE) (0.173, 0.245). The performance of the device without TPBI is as follows: start-up voltage 3.5 volts, maximum brightness 1265cd/m ² , maximum current efficiency 0.71cd/A, maximum external quantum efficiency 0.74%, color coordinates (CIE) (0.226, 0.284). Its electroluminescent spectrum is shown in Figure 5 and Figure 6.

Example 3

The first seven steps of the present embodiment are the same as the first seven steps of Embodiment 1.

Step 8: Preparation of 2-carbazole-7-nitro-9,9-dioctylfluorene

3,5-2-nitro-7-bromo-9,9-dioctylfluorene (1.03g, 2mmol), carbazole (0.334g, 2mmol) were added to a 50ml three-necked flask under an argon atmosphere. , potassium carbonate (0.849g, 6mmol), dimethylsulfoxide 30ml, copper powder (5g, 78mmol). After stirring evenly, the temperature was raised to 150° C. for 12 hours of reaction. After cooling, it was extracted with dichloromethane, washed three times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. For column separation, the mobile phase used is dichloromethane/petroleum ether=1:8, remove the raw material point, dichloromethane/petroleum ether=1:4, collect the second point. Obtained 0.320 g of brown-yellow solid. Yield 26.7%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.36-8.34 (m, 1H), 8.28 (s, 1H), 8.20 (d, 2H), 8.04-8.02 (m, 1H), 7.91-7.88 (m, 1H), 7.67-7.63(m, 2H), 7.45(s, 4H), 7.37-7.32(m, 2H), 2.09(m, 4H), 1.28-1.12(m, 20H), 0.85-0.80 (t, 6H), 0.74(m, 4H).

Step 10: Preparation of 2-amino-7-carbazole-9,9-dioctylfluorene

The method is the same as step three, only need to replace 2-nitro-9,9-dioctylfluorene with 2-carbazole-7-nitro-9,9-dioctylfluorene (0.32g, 0.53mmol) to obtain green Yellow viscous body 0.179g, yield 58.9%.

¹ H NMR (300MHz, DMSO), δ (ppm): 8.24 (m, 2H), 7.76 (m, 1H), 7.52 (m, 2H), 7.41 (m, 3H), 7.30 (m, 4H), 6.60 (m, 2H), 5.30(s, 2H), 2.10-1.75(m, 4H), 1.40-0.90(m, 20H), 0.90-0.500(m, 10H).

Step 11: Preparation of bis(7-bromo-9,9-dioctylfluorene-2-)-(7-(9-carbazole)-9,9-dioctylfluorene-2-)amine

Under argon atmosphere, into a 50ml three-necked flask, add 2,7-dibromo-9,9-dioctylfluorene (0.966g, 1.75mmol), 2-amino-7-carbazole-9,9- Dioctylfluorene (0.179g, 0.35mmol), dissolved in 15ml of toluene. Further _Pd2 (dba) ₃ (0.0090 g, 0.00875 mmol), DPPF (0.0214 g, 0.035 mmol), ^tBuONa (0.390 g, 3.48 mmol) were added. The reaction was carried out at 110° C. for 24 hours. After natural cooling, it was extracted with ethyl acetate, washed three times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. For column separation, the mobile phase used was petroleum ether/dichloromethane=1:6, 1:3. After drying in vacuo, 0.325 g of the product orange-yellow viscous body was obtained, with a yield of 68.9%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.19-8.16 (m, 2H), 7.80 (m, 1H), 7.63-7.60 (m, 1H), 7.54-7.42 (m, 12H), 7.32 -7.26(m, 4H), 7.26-7.25(m, 3H), 7.05-7.03(m, 3H).1.88(m, 12H), 1.25-1.09(m, 60H), 0.86-0.68(m, 30H) .

Step 12: Preparation of polymer P4FNCz

Under an argon atmosphere, add the raw material bis(7-bromo-9,9-dioctylfluorene-2-)-(7-(9-carbazole)-9,9-dioctyl to a 50ml three-necked flask Fluorene-2-)amine (0.246g, 0.163mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-)-9,9 -Dioctylfluorene (0.106g, 0.163mmol), Et ₄ NOH 1ml, and dilute with 1ml of deionized water, add catalyst Pd(pph ₃ ) ₄ (0.0048g, 0.00415mmol), toluene 5ml, after 30 minutes of passing Ar, gradually Raise the temperature to 90-100°C and react for 48 hours. Cool naturally, add phenylboronic acid (11.2mg, 0.0918mmol), toluene 2ml, and react for 12 hours. After natural cooling, 1ml of bromobenzene (9.6mmol) was added and reacted for 12 hours. The resulting viscous was dissolved with toluene, precipitated with methanol, and dried. Then, they were extracted with methanol, acetone, and tetrahydrofuran for 24 hours, concentrated, precipitated in methanol, filtered, and dried in vacuo. Obtained 0.233g, yield 75.5%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.20-8.16 (m, 2H), 7.90-7.75 (m, 4H), 7.74-7.57 (m, 12H), 7.56-7.48 (m, 3H) , 7.47-7.37(m, 5H), 7.36-7.27(m, 4H), 7.20-6.90(m, 2H), 2.30-1.80(m, 16H), 1.40-1.00(m, 80H), 0.99-0.50( m, 40H).

The absorption spectrum and fluorescence spectrum of the polymer film are shown in Fig. 3 and Fig. 4 .

The implementation steps of the device are the same as those in Embodiment 1. The performance of the device is as follows: start-up voltage 3.0V, maximum brightness 1265cd/m ² , maximum current efficiency 1.34cd/A, maximum external quantum efficiency 1.67%, color coordinates (CIE) (0.164, 0.125). The performance of the device without TPBI is as follows: start-up voltage 3.0 volts, maximum brightness 1241cd/m ² , maximum current efficiency 0.49cd/A, maximum external quantum efficiency 0.62%, color coordinates (CIE) (0.192, 0.220). Its electroluminescent spectrum is shown in Figure 5 and Figure 6.

Example 4

The first ten steps of this embodiment are the same as the first ten steps of Embodiment 2.

Step 11: Bis(7-bromo-9,9-dioctylfluorene-2-)-(7-(2-oxadiazole(5-benzene))-9,9-dioctylfluorene-2- ) Preparation of amine

Under an argon atmosphere, add bis(7-bromo-9,9-dioctylfluorene-2-)-(7-cyano-9,9-dioctyl) dissolved in 30 ml of freshly distilled DMF into a 50 ml three-necked flask Difluoren-2-)amine (0.7397g, 0.542mmol), sodium azide (0.224g, 3.45mmol), ammonium chloride (0.1953g, 3.65mmol). After stirring evenly, react at 100° C. for 36 hours. Cool naturally, add hydrochloric acid until acidic, and a solid precipitates out. After suction filtration, it was found that the resulting filtrate also had product. Then, it was extracted with ethyl acetate, washed three times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. Column separation, the mobile phase used (petroleum ether/dichloromethane=1:6 to remove the raw material and recover, 1:4 to obtain the product point) was spin-dried, and vacuum-dried to obtain 0.3652 g of the intermediate tetrazole. In a 50ml three-neck flask, under an argon atmosphere, dissolve tetrazole (0.342g, 0.24mmol) with 40ml of anhydrous pyridine, add dropwise benzoyl chloride (2ml, 4.26mmol), the color becomes orange, and reflux for 3 days . Naturally cooled, extracted with ethyl acetate, washed 3 times with saturated brine, and the obtained organic layer was dried over anhydrous magnesium sulfate. After suction filtration, the resulting filtrate was freed of solvent under reduced pressure. Column separation, mobile phase: petroleum ether/dichloromethane=10:1, 8:1, 6:1, 5:1, 4:1, spin-dried, vacuum-dried to obtain 0.413g, and the average yield of the two-step reaction was 51.4 %.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.20-8.17 (m, 2H), 8.11-8.09 (m, 2H), 7.75-7.72 (m, 1H), 7.61-7.43 (m, 11H) , 7.27-7.26(m, 2H), 7.25-7.24(m, 2H), 7.04-7.01(m, 3H), 2.07-1.80(m, 12H), 1.43-1.08(m, 60H), 0.99-0.69( m, 30H).

Step 12: Preparation of polymer P4FNOXDPh

Under Ar atmosphere, add raw material bis(7-bromo-9,9-dioctylfluorene-2-)-(7-(2-oxadiazole(5-benzene))-9 to a 50ml three-necked flask, 9-dioctylfluoren-2-)amine (0.2986g, 0.20mmol), 2,7-di(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2- )-9,9-dioctylfluorene (0.1306g, 0.20mmol), Et ₄ NOH 1.5ml, and diluted with 1.5ml deionized water, catalyst palladium acetate 1.9mg, tricyclohexylphosphine 4.0mg toluene 7ml. After passing Ar for 30 minutes, the temperature was gradually raised to 90-100°C. React for 48 hours. Cool naturally, add phenylboronic acid (0.0107g, 0.0088mmol), toluene 2ml, and react for 10 hours. Cool naturally, add bromobenzene (0.5ml, 4.8mmol), and react for 10 hours. Cool naturally, precipitate with methanol, filter, and dry in vacuo, then extract with methanol, acetone, and THF for 24 hours, concentrate, precipitate with methanol, filter, and dry in vacuo. 246.3mg was obtained, the yield was 65.4%.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.24-8.04 (m, 4H), 7.87-7.50 (m, 18H), 7.40-7.27 (m, 4H), 7.16-7.03 (m, 3H) , 2.30-1.76(m, 16H), 1.40-1.00(m, 80H), 0.99-0.43(m, 40H).

The absorption spectrum and fluorescence spectrum of the polymer film are shown in Fig. 3 and Fig. 4 .

The implementation steps of the device are the same as those in Embodiment 1. The performance of the device is as follows: start-up voltage 2.9V, maximum brightness 4824cd/m ² , maximum current efficiency 4.1cd/A, maximum external quantum efficiency 2.8%, color coordinates (CIE) (0.181, 0.301). The performance of the device without TPBI is as follows: start-up voltage 3.0 volts, maximum brightness 4456cd/m ² , maximum current efficiency 1.05cd/A, maximum external quantum efficiency 0.66%, color coordinates (CIE) (0.193, 0.352). Its electroluminescent spectrum is shown in Figure 5 and Figure 6.

Example 5

The first eight steps of the present embodiment are the same as the first eight steps of Embodiment 1.

Step 9: Preparation of polymer PSFOFN5

Under Ar atmosphere, add raw material bis(7-bromo-9,9-dioctylfluorene-2-)-(9,9-dioctylfluorene-2-)amine (0.0671g, 0.05mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-)-9,9-dioctylfluorene (0.3239g, 0.50 mmol), 2,7-dibromo-9,9-dioctylfluorene (0.1912g, 0.35mmol), 2,7-dibromodibenzothiophene-S,S-diox (0.0383mg, 0.10mmol) , Et ₄ NOH 1.7ml, and diluted with 1.7ml deionized water, catalyst palladium acetate 1.8mg, tricyclohexylphosphine 6.4mg, toluene 8ml. After passing Ar for 30 minutes, the temperature was gradually raised to 90-100°C. React for 48 hours. Cool naturally, add phenylboronic acid (0.0157g, 0.0129mmol), toluene 2ml, and react for 10 hours. Cool naturally, add bromobenzene (0.5ml, 4.8mmol), and react for 10 hours. Cool naturally, precipitate with methanol, filter, and dry in vacuo, then extract with methanol, acetone, and THF for 24 hours, concentrate, precipitate with methanol, filter, and dry in vacuo. Yield 219.2mg.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.20-7.90 (m, 4H), 7.89-7.79 (m, 7H), 7.78-7.50 (m, 14H), 2.12 (m, 16H), 1.33 -1.03(m, 80H), 0.96-0.50(m, 40H).

The absorption spectrum and fluorescence spectrum of the polymer film are shown in Fig. 9 and Fig. 10 respectively.

Example 6

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300 MHz, CDCl ₃ ), (ppm): 7.83 (m, 7H), 7.72-7.61 (m, 16H), 7.49-7.47 (m, 1H), 7.38-7.28 (m, 1H), 2.11 ( m, 16H), 1.25-0.96(m, 80H), 0.84-0.50(m, 40H).

Example 7

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.89-7.78 (m, 7H), 7.77-7.55 (m, 16H), 7.52-7.47 (m, 1H), 7.40-7.28 (m, 1H) , 2.11(m, 16H), 1.30-0.98(m, 80H), 0.96-0.50(m, 40H).

Example 8

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.88-7.80 (m, 6H), 7.79-7.52 (m, 16H), 7.45-7.29 (m, 3H), 2.27 (m, 16H), 1.35 -1.02(m, 80H), 0.98-0.50(m, 40H).

The implementation steps of the device are the same as those in Embodiment 1. The performance of the device is as follows: start-up voltage 3.2V, maximum brightness 2465cd/m ² , maximum current efficiency 3.36cd/A, maximum external quantum efficiency 4.64%, and color coordinates (CIE) of (0.152, 0.102). The performance of the device without TPBI is as follows: start-up voltage 3.2 volts, maximum brightness 7695cd/m ² , maximum current efficiency 1.68cd/A, maximum external quantum efficiency 1.97%, color coordinates (CIE) (0.182, 0.198).

Example 9

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 8.20-7.95 (m, 3H), 7.94-7.77 (m, 7H), 7.76-7.54 (m, 15H), 2.11 (m, 16H), 1.33 -1.03(m, 80H), 0.96-0.50(m, 40H).

Example 10

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.89-7.77 (m, 5H), 7.76-7.51 (m, 15H), 7.40-7.27 (m, 3H), 7.19-6.81 (m, 2H) , 2.10(m, 16H), 1.33-1.01(m, 80H), 0.93-0.50(m, 40H).

Example 11

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.90-7.76 (m, 5H), 7.75-7.51 (m, 14H), 7.41-7.28 (m, 4H), 7.17-6.95 (m, 2H) , 2.10(m, 16H), 1.32-1.01(m, 80H), 0.95-0.50(m, 40H).

Example 12

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.91-7.75 (m, 4H), 7.74-7.53 (m, 15H), 7.42-7.29 (m, 4H), 7.23-7.07 (m, 2H) , 2.08(m, 16H), 1.31-1.01(m, 80H), 0.92-0.50(m, 40H).

Example 13

This implementation step is the same as that of Example 5, and the proportioning of the monomers used is shown in Table 1 below.

¹ H NMR (300MHz, CDCl ₃ ), δ (ppm): 7.89-7.76 (m, 3H), 7.75-7.51 (m, 14H), 7.41-7.29 (m, 5H), 7.18-6.97 (m, 3H) , 2.08(m, 16H), 1.32-1.01(m, 80H), 0.95-0.50(m, 40H).

Table 1

It can be seen from Figure 1 and Figure 2 that the maximum absorption peaks of the four polymers P4FN, P4FNCN, P4FNCz, and P4FNOXDPh in toluene solution are all around 410nm, and the main peaks of their fluorescence spectra are all in the blue light region. It can be seen from Figure 7 and Figure 8 that the maximum absorption peak of polymer PSFOFN1-PSFOFN50 in toluene solution is around 390nm, and the main peak of its fluorescence spectrum is in the blue light region, and with the increase of the content of trifluorenamine compound in the polymer, the absorption Both the fluorescence spectrum and the fluorescence spectrum show a certain red shift. It can be seen from Figure 3 and Figure 4 that the maximum absorption peaks of the four polymers in the solid film state are all around 220nm, and the main peaks of their fluorescence spectra are all in the blue light region. From Figure 9 and Figure 10, it can be seen that in the state of solid film, with the increase of the content of trifluorenamine compounds in polymers PSFOFN1~PSFOFN50, the maximum absorption peak changes from about 390nm to about 220nm, showing a certain regularity , the main peak of its fluorescence spectrum is in the blue region. It can be seen from Figure 5, Figure 6, Figure 11, and Figure 12 that the main peaks of the electroluminescence spectra of this series of polymers are all in the blue light region.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (2)

1. a trifluorene amine compound, is characterized in that, this compound has following chemical structure:

Wherein: R ₁ is a solubilizing alkyl or alkoxy group, and the number of carbon atoms is 1 to 20; the structure of X is as follows:

The structure of Ar is:

2. according to the preparation method of the described trifluorene amine compound of claim 1, it is characterized in that, comprises the steps: Add 2-amino-9,9-dioctylfluorene inducer and 2,7 -Dibromo-9,9-dioctylfluorene, dissolved in toluene, and then added Pd ₂ (dba) ₃ ,1 /10 DPPF and 10 times ^tBuONa , reacted for 24 to 36 hours under heating and reflux, cooled naturally after the reaction, extracted with ethyl acetate, and washed with saturated brine, and the organic layer was dried with anhydrous magnesium sulfate, Suction filtration, the obtained filtrate removes the solvent under reduced pressure, separates through a chromatographic column, evaporates the solvent and vacuum-dries to obtain a trifluorene amine compound.

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