CN100543059C - White electroluminescent macromolecule material and preparation method thereof - Google Patents

Abstract

The invention belongs to a kind of white electroluminescent macromolecule material and preparation method thereof.Based on the physical thought that in single polymer, can realize white light emission by the relative luminous intensity of regulation and control blue emission and orange Optical Transmit Unit, adopting poly-fluorenes and derivative thereof is blue light structure primitive, naphthalimide derivative is orange light structure primitive, by Yamamoto or Suzuki reaction naphthalimide derivative is copolymerized to poly-fluorenes and derivative main chain and end-blocking thereof the make to poly-fluorenes and derivative end group thereof, and the relative content of adjusting blue emission primitive and orange light emission primitive, realize that blue light and orange light emission primitive are independent luminous in single polymer, construct molecule dispersion type white light polymer material.

Description

White electroluminescence polymer material and preparation method thereof

This application is a divisional application of an invention patent application with application number "200410010770.0", application date "March 29, 2004", and invention title "white electroluminescent polymer material and its preparation method".

technical field

The invention belongs to a white electroluminescent polymer material and a preparation method thereof.

technical background

Since Burroughs et al. of the University of Cambridge reported the electroluminescence phenomenon of poly(p-phenylene vinylene) (PPV) for the first time in 1990, polymer electroluminescent materials and devices have the advantages of simple process and easy realization of large-screen display and flexible display. And other outstanding features have attracted extensive attention and investment from academia and industry. At present, representative blue, green and red polymer luminescent material systems such as polyphenylene (PPP), polyalkylfluorene (PAF), polyphenylene vinylene (PPV), and polythiophene (PAT) have been developed. In addition, the performance indicators of its monochromatic polymer electroluminescence devices meet the practical requirements. In contrast, the performance indicators of white light polymer devices are far from the practical requirements, and it needs to be studied from both material design and device structure. In-depth research is carried out on each aspect to accelerate the practical process of white light polymer devices.

The realization of white light polymer electroluminescent devices mainly includes three aspects:

(1) organic luminescent dye/polymer blend system; (2) polymer/polymer blend system; (3) single polymer white light system. For example: J.Kido etc. (Appl.Phys.Lett., 64,815,1994) disperse three kinds of fluorescent dyes of red, green and blue in polyvinylcarbazole (PVK), realize by adjusting the content of three kinds of dyes White light emission, the maximum brightness can reach 3400cd/m ² ; Inganas et al. (Appl. Phys. Lett., 68, 147, 1996) blended red, green and blue polythiophene derivatives with inert polymers such as PMMA , at a high driving voltage (20V), white emission with CIE of (0.220, 0.466) was obtained. However, due to the obvious phase separation between polymers and polymers in this system, the white light emission is voltage-dependent, and it is difficult to obtain stable white light devices. The Leising research group dispersed a small amount (0.66wt%) of red light polymer (PPDB) into a high-efficiency blue light polyfluorene derivative (m-LPPP) with a ladder structure. Due to the formation of a homogeneous polymer/polymer blend system, The voltage dependence of the white light color purity is improved to a certain extent, and a white light polymer device with an external quantum efficiency of 1.2% is obtained. Regarding the single polymer white light system (Appl. Phys. Lett., 79, 308, 2001 and Macromolecules, 35, 6782, 2002), it is mainly based on the formation of radical excitation recombination of blue or blue-green light PPV polymers in the process of electroluminescence matter, resulting in broadband luminescence, therefore, its white light polymer devices not only have obvious color voltage dependence, but also have poor performance.

Contents of the invention

The purpose of the present invention is to provide a white electroluminescent polymer material;

The second object of the present invention is to provide a preparation method of a white electroluminescence polymer material.

The present invention is based on the physical idea that white light emission can be realized by adjusting the relative luminous intensity of blue light emission and orange light emission units in a single polymer, and provides a high-efficiency and stable white electroluminescent polymer material system of main chain type and end group type .

In the invention, polyfluorene and its derivatives are used as blue-light structural units, and naphthalimide derivatives are used as orange-light structural units.

The single white light polymer luminescent material provided by the present invention has the following basic structure:

End group type single white light polymer luminescent material:

Wherein: _R1 is independently selected from hexyl, octyl, phenyl, fluorenyl, or selected from hexyl substituted phenyl, hexyl substituted fluorenyl, octyl substituted phenyl or octyl substituted fluorenyl;

Ar1 is a naphthalimide derivative unit, selected from one or more of the following structural units:

Wherein: _R3 is independently selected from methyl, butyl, hexyl, octyl, decyl or aryl; _R4 is independently selected from methyl, butyl or aryl; wherein aryl is independently selected from phenyl, Naphthyl, butyl or tert-butyl substituted phenyl or naphthyl; _R independently selected from hydrogen, methyl or methoxy;

Ar2 is an electron transport unit or a hole transport unit, selected from one or more of the following structural units:

Wherein: R is _{independently} selected from methyl, butyl or tert-butyl;

x and y are the content of each element, satisfying 0<x<1, 0<y<1, x+y=1, n is an integer greater than 1 and less than or equal to 300.

The preparation method of the white electroluminescent polymer material provided by the present invention comprises (A) preparation of monomers and (B) preparation of polymers;

(A) Preparation of monomer

The preparation of monobromonaphthalimide derivative monomer, its structural general formula is:

Where Ar1 is the same as Ar1 in the end-group single white light polymer material;

The preparation method of monobromonaphthalimide derivative monomer is as follows:

Dissolve the naphthalimide derivative Ar1H and tetrabutylammonium tribromide with a molar ratio of 1-2 times in dichloromethane, react at room temperature for 10-1200 minutes, pour the reaction product into water, separate the organic phase, repeat After washing several times with water, drying, concentrating, and recrystallizing, monobromonaphthalimide derivative monomers are obtained;

(B) Preparation of polymer

Preparation of terminal-type white light polymer materials

The preparation of end-type white light polymer materials adopts Yamamoto and Suzuki polymerization, and its preparation method is as follows:

Yamamoto polymerization reaction: under the protection of nitrogen, 2,7-dibromofluorene derivative monomer and 0%<molar ratio≤30% bibromoaromatic monomer Ar2 are dissolved in anhydrous toluene, and then added dropwise to In a DMF solution with a molar ratio of 2-3 times Ni(O), react at a temperature of 50-100° C. for 24-120 hours and then add 0.01%-10% molar ratio of monobromonaphthalimide derivative monomer, Continue to react at a temperature of 50-100°C for 1-48 hours, use a methanol/concentrated hydrochloric acid mixed solution to terminate the reaction, extract and separate, concentrate and precipitate, solvent extract, and vacuum dry to obtain a fibrous polymer luminescent material;

Suzuki polymerization reaction: Dissolve 2,7-bisboronate fluorene derivative monomer and 0.0001%-30% molar ratio of bisbrominated aromatic monomer Ar2 in toluene, and then add 2.0M potassium carbonate with a molar ratio of 3 times solution, under nitrogen protection and a temperature of 50-100°C, add 0.050% molar ratio of tetrakis(triphenylphosphine) palladium, and add 0.01%-10% molar ratio of monobromonaphthoyl after reacting for 24-120 hours Amine derivative monomers, continue to react at 50-100°C for 1-48 hours, use 0.1M dilute hydrochloric acid solution to terminate the reaction, extract with chloroform, settle with methanol, extract with solvent, and dry in vacuum to obtain fibrous polymer materials .

Detailed ways

Embodiment 1: Synthesis of 4-bromo-9-(4-tert-butylphenyl)-1,8-naphthalimide

Under the protection of nitrogen, 4-bromo-1,8-naphthalene dianhydride (10.0 g, 36.2 mmol), p-tert-butylaniline (6.0 g, 40.1 mmol), and 120 ml of acetic acid were added into the reaction flask as a solvent. React at 130° C. for 10 hours under magnetic stirring. Pour into water, filter, wash with water several times, and separate the product by column chromatography to obtain 8.10 g of 4-bromo-9-(4-tert-butylphenyl)-1,8-naphthalimide, a white solid, with a yield of 55% .

Embodiment 2: 4-N, the synthesis of N-diphenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide

Under nitrogen protection, 4-bromo-9-(4-tert-butylphenyl)-1,8-naphthalimide (4.48g, 11.0mmol), diphenylamine (1.69g, 10.0mmol), anhydrous carbonic acid To the mixture of potassium (1.53g, 11.0mmol), cuprous iodide (0.096g, 0.50mmol), and 18-crown-6 (0.13g, 0.50mmol), 3ml of DMPU solvent was added. React at 190° C. for 20 hours under magnetic stirring. Extract the product with dichloromethane, wash with acid, wash with ammonia, wash with water several times, and separate the product by column chromatography to obtain the product 4-N,N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthoyl Imine 1.74g, orange-red solid, yield 35%.

Embodiment 3: 4-N, the synthesis of N-bis(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide

4-N, N-diphenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (1.49g, 3.0mmol), tetrabutylammonium tribromide (2.87g, 6.6 mmol) was dissolved in 50 ml of dichloromethane, reacted at room temperature for 10 minutes, poured into water, washed the organic layer several times, and separated the product by column chromatography to obtain the pure intermediate product 4-N, N-(4-bromophenyl)-9 -(4-tert-butylphenyl)-1,8-naphthoylidene 1.91 g, orange-red solid, yield 97%.

Example 4: Synthesis of 4-carbazolyl-9-(4-tert-butylphenyl)-1,8-naphthalimide

Under nitrogen protection, 4-bromo-9-(4-tert-butylphenyl)-1,8-naphthalimide (4.48g, 11.0mmol), carbazole (1.67g, 10.0mmol), anhydrous To the mixture of potassium carbonate (1.53g, 11.0mmol), cuprous iodide (0.096g, 0.50mmol), and 18-crown-6 (0.13g, 0.50mmol), 3ml of DMPU solvent was added. React at 190° C. for 20 hours under magnetic stirring. Extract the product with dichloromethane, wash with acid, wash with ammonia, wash with water several times, and separate the product by column chromatography to obtain the pure product 4-carbazolyl-9-(4-tert-butylphenyl)-1,8-naphthalimide , yellow solid 1.22g, yield 25%.

Example 5: Synthesis of 4-(4,4'-dibromocarbazolyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide

4-carbazolyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.99g, 2.0mmol), tetrabutylammonium tribromide (3.82g, 8.0mmol) were dissolved In 30 ml of dichloromethane, react at room temperature for 20 hours, pour into water, wash the organic layer several times, and separate the product (dichloromethane) by column chromatography to obtain the pure intermediate product 4-N,N-(4-bromocarbazolyl )-9-(4-tert-butylphenyl)-1,8-naphthalimide 1.24 g, yellow solid, yield 95%.

Embodiment 6: 4-N, the synthesis of N-bis(4-formylphenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide

Under an ice-salt bath, POCl ₃ (32.8 g, 214 mmol) was added dropwise into DMF (15.6 g, 214 mmol), and stirred for 30 minutes. Then 4-N-(4-formylphenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (1.40 g, 2.67 mmol) was added dropwise DMF solution, gradually heated up to 100°C, and reacted for 100 hours. Washed with water, extracted with dichloromethane, washed repeatedly, dried, filtered, and the product was separated by column chromatography to obtain 0.34 g of the product with a yield of 23%.

Example 7: Synthesis of 4-N, N-bis(4-bromostyryl) phenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide

4-N, N-bis(4-formylphenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.34g, 0.62mmol), 4-bromo-bromo Tributylphosphinomethylenebenzene (0.62g, 1.37mmol) was dissolved in chloroform (20ml), then, a solution of sodium metal (0.091g, 3.91mmol) in ethanol (5ml) was added dropwise, and reacted at room temperature for 10 hours. The reaction was terminated by adding dilute hydrochloric acid solution, extracted with chloroform, washed repeatedly, dried, filtered, and separated by column chromatography to obtain 0.37 g of the product with a yield of 69%.

Example 8: 4-N, N-(4,4'-bis-(4-(p-tolylphenylamino)phenyl)-9-(4-tert-butylphenyl)-1,8- Synthesis of Naphthalimide

Under the protection of nitrogen, add 4-N, N-bis(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.65g, 0.99 mmol), 4-N, N-p-tolylphenylaminophenylboronate (0.85g, 2.2mmol), anhydrous potassium carbonate (1.60g, 0.9mmol), toluene (10ml), water ( 10ml) and palladium catalyst (30mg), reacted at 80°C for 48 hours under magnetic stirring. The product was extracted with dichloromethane, washed once with 1N hydrochloric acid, washed with ammonia water until the aqueous layer was colorless, washed several times with water, dried over _{anhydrous Na2SO4} , concentrated, and separated by silica gel column chromatography to obtain a red solid 0.69g, yield 69% .

Example 9: 4-N, N-(4,4'-bis-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9-(4-tert-butylphenyl)- Synthesis of 1,8-naphthalimide

4-N, N-(4,4'-bis-(4-(p-tolylphenylamino)phenyl)-9-(4-tert-butylphenyl)-1,8-naphthoylidene Amine (0.51g, 0.50mmol), tetrabutylammonium tribromide (0.53g, 1.1mmol) were dissolved in 10 ml of dichloromethane, reacted at room temperature for 10 minutes, poured into water, washed the organic layer several times, and separated by column chromatography Product, 0.55 g of the product was obtained as an orange-red solid, and the yield was 95%.

Example 10: Synthesis of 9-phenyl-9-(4-bromomethylphenyl)-2,7-dibromofluorene

Add 9-phenyl-9-(4-methylphenyl)-2,7-dibromofluorene (0.90g, 1.84mmol), NBS (0.33g, 1.84mmol), BPO (0.044g , 0.184mmol) and 10ml carbon tetrachloride, reacted under reflux conditions for 2 hours, filtered after cooling, and the filtrate was drained to obtain pure intermediate product 9-phenyl-9-(4-bromomethylphenyl)-2,7- Dibromofluorene 0.94g, off-white solid, yield 90%.

Example 11: Synthesis of 9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene

Add tributylphosphine (0.65ml, 2.55mmol) to the reaction flask, raise the temperature to 100°C under nitrogen protection, then add 9-phenyl-9-(4-bromomethylphenyl)-2,7 - Mixed solution of dibromofluorene (1.00g, 1.76mmol) and 15ml DMF, heated to 140°C for 24 hours, cooled to room temperature, poured into diethyl ether and stirred, and repeated three times to obtain the pure intermediate product 9-phenyl -9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene 0.89 g, off-white powder, yield 64%.

Example 12: 9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-phenyl-9-(4-tert-butylphenyl) Synthesis of -1,8-naphthoimido)-2,7-dibromofluorene

9-Phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene (0.49g, 0.64mmol) and 4-N-(4-aldehyde phenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.34g, 0.64mmol) was dissolved in chloroform (15ml), then added dropwise Sodium metal (0.058g, 2.560mmol) in ethanol (5ml) was reacted at room temperature for 10 hours. Add dilute hydrochloric acid solution to terminate the reaction, extract with chloroform, wash repeatedly, dry, filter, and separate the product by column chromatography to obtain the pure intermediate product 9-phenyl-9-((4-N-(4-(4'-styryl) Phenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthoimido)-2,7-dibromofluorene 0.46g, red solid, yield 72%.

Example 13: 4-N-(4-formylphenyl)-4-N-(4-(4'-styryl)phenyl)-9-(4-tert-butylphenyl)-1, Synthesis of 8-naphthalimide

Tributylphosphinomethylenebenzene bromide (0.37g, 1.00mmol) and 4-N,N-bis(4-formylphenyl)-9-(4-tert-butylphenyl)-1, 8-Naphthimide (0.55g, 1.00mmol) was dissolved in chloroform (25ml), then a solution of sodium metal (0.092g, 4.000mmol) in ethanol (5ml) was added dropwise, and reacted at room temperature for 20 hours. Add dilute hydrochloric acid solution to terminate the reaction, extract with chloroform, wash repeatedly, dry, filter, and separate the product by column chromatography to obtain the pure intermediate product 4-N-(4-formylphenyl)-4-N-(4-(4'- Styryl)phenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide 0.41 g, red solid, yield 65%.

Example 14: 9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-((4'-styryl)phenyl)-9 Synthesis of -(4-tert-butylphenyl)-1,8-naphthoimido)-2,7-dibromofluorene

9-Phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene (0.61g, 0.80mmol) and 4-N-(4-aldehyde phenyl)-4-N-(4-(4'-styryl)phenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (1.00g, 1.60mmol ) was dissolved in chloroform (20ml), then a solution of sodium metal (0.185g, 8.0mmol) in ethanol (5ml) was added dropwise, and reacted at room temperature for 50 hours. Add dilute hydrochloric acid solution to terminate the reaction, extract with chloroform, wash repeatedly, dry, filter, and separate the product by column chromatography to obtain the pure intermediate product 9-phenyl-9-((4-N-(4-(4'-styryl) Phenyl)-4-N-((4'-styryl)phenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide)-2,7-dibromo Substituted fluorene 0.62g, red solid, yield 70%.

Example 15: 2-(2'-(4'-amino-1',8'-naphthalimide-9'-alkyl)ethoxy)-5-hexyloxy-1,4-dibromo Synthesis of Benzene

Under the protection of a nitrogen atmosphere, 1.06g (5mmol) of 4-amino-1,8-naphthalimide was dissolved in 60 milliliters of dimethyl sulfoxide, and then 2.8g (50mmol) of powdered potassium hydroxide was added to the solution, Under electromagnetic stirring, react at 150°C for ten minutes, then gradually add 2.31g (5mmol) 2-(2-bromoethoxy)-5-hexyloxy-1,4-dibromobenzene to the system, and react for 1 hour. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 2.06 g of a pure intermediate product with a yield of 70%.

Example 16: 2-(2'-(4'-dianilino-1',8'-naphthalimide-9'-alkyl)ethoxy)-5-hexyloxy-1,4- Dibromobenzene

2-(2'-(4'-amino-1',8'-naphthalimide-9'-alkyl)ethoxy)-5-hexyloxy-1,4-dibromobenzene (0.589g , 1.0mmol), iodobenzene (0.41g, 2.0mmol), potassium carbonate (0.28g, 2.0mmol), 18-crown-6 (0.003g, 0.01mmol), cuprous iodide (0.002g, 0.01mmol), DMPU 0.30mL was heated to 200°C under nitrogen protection for 5 hours. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 0.33 g of a red solid with a yield of 45%.

Example 17: 2-(12'-(4'-amino-1',8'-naphthalimide-9'-alkyl)dodecyloxy)-5-hexyloxy-1,4- Synthesis of Dibromobenzene

Under the protection of nitrogen atmosphere, 1.06g (5mmol) 4-amino-1,8-naphthoimide was dissolved in 60 milliliters of dimethylsulfoxide, and then 0.28g (5mmol) of powdered potassium hydroxide was added to the solution, Under electromagnetic stirring, react at 50°C for ten minutes, then gradually add 30.0g (50mmol) 2-(12-bromododecyloxy)-5-hexyloxy-1,4-dibromobenzene to the system, and react for 120 Hours, chloroform extraction, repeated washing, drying, filtration, and column chromatography to separate the product to obtain 2.906 g of pure intermediate product with a yield of 81%.

Example 18: 2-(12'-(4'-dianilino-1',8'-naphthalimide-9'-alkyl)dodecyloxy)-5-hexyloxy-1, 4-Dibromobenzene

2-(12'-(4'-amino-1',8'-naphthalimide-9'-alkyl)dodecyloxy)-5-hexyloxy-1,4-dibromobenzene ( 0.7369g, 1.0mmol), iodobenzene (4.08g, 10.0mmol), potassium carbonate (2.8g, 20.0mmol), 18-crown-6 (0.015g, 0.05mmol), cuprous iodide (0.0095g, 0.05mmol) ), DMPU 0.30mL was heated to 140°C under nitrogen protection for 50 hours. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 0.283 g of a red solid with a yield of 33%.

Example 19: 9,9-bis(2-(4-amino-1,8-naphthalimide-9-)ethyl)-2,7-dibromofluorene

Under the protection of a nitrogen atmosphere, 1.06g (5mmol) of 4-amino-1,8-naphthalimide was dissolved in 60 milliliters of dimethyl sulfoxide, and then 2.8g (50mmol) of powdered potassium hydroxide was added to the solution, Under electromagnetic stirring, react at 150°C for ten minutes, then gradually add 1.34g (2.5mmol) 9,9-bis(2-bromoethyl)-2,7-dibromofluorene to the system, react for 1 hour, and extract with chloroform After repeated washing, drying, filtering, and column chromatography to separate the product, 1.40 g of a pure intermediate product was obtained with a yield of 70%.

Example 20: 9,9-bis(2-(4-diphenylamino-1,8-naphthalimide-9-)ethyl)-2,7-dibromofluorene

9,9-bis(2-(4-amino-1,8-naphthalimide-9-)ethyl)-2,7-dibromofluorene (0.400g, 0.5mmol), iodobenzene (0.41 g, 2.0mmol), potassium carbonate (0.414g, 3.0mmol), 18-crown-6 (0.015g, 0.05mmol), cuprous iodide (0.0095g, 0.05mmol), DMPU0.30mL was heated to React at 200°C for 5 hours. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 0.138 g of a red solid with a yield of 25%.

Example 21: 9,9-bis(12-(4-amino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene

Under the protection of a nitrogen atmosphere, 1.6g (7.5mmol) of 4-amino-1,8-naphthalimide was dissolved in 60ml of dimethyl sulfoxide, and then 0.28g (5mmol) of powdered potassium hydroxide was added to the solution , reacted at 50°C for ten minutes under electromagnetic stirring, then gradually added 2.04g (2.5mmol) 9,9-bis(12-bromododecyl)-2,7-dibromofluorene to the system, and reacted for 120 hours , extracted with chloroform, washed repeatedly, dried, filtered, and separated by column chromatography to obtain 2.00 g of pure intermediate product with a yield of 74%.

Example 22: 9,9-bis(12-(4-diphenylamino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene

9,9-bis(2-(4-amino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene (0.540g, 0.5mmol), iodobenzene (2.04g, 10mmol), potassium carbonate (1.38g, 10mmol), 18-crown-6 (0.003g, 0.01mmol), cuprous iodide (0.002g, 0.01mmol), DMPU0.30mL was heated to React at 140°C for 50 hours. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 0.221 g of a red solid with a yield of 32%.

Example 23: 2-(6'-(4'-amino-1',8'-naphthalimide-9'-alkyl)hexyloxy)-5-hexyloxy-1,4-dibromo Synthesis of Benzene

Under the protection of a nitrogen atmosphere, 2.12g (10mmol) of 4-amino-1,8-naphthalimide was dissolved in 60 milliliters of dimethyl sulfoxide, and then 0.56g (10mmol) of powdered potassium hydroxide was added to the solution, Under electromagnetic stirring, react at 120°C for ten minutes, then gradually add 5.17g (10mmol) 2-(6-bromohexyloxy)-5-hexyloxy-1,4-dibromobenzene to the system, and react for 14 hours. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 3.94 g of a pure intermediate product with a yield of 61%.

Example 24: 2-(6'-(4'-Dianilino-1',8'-naphthalimide-9'-alkyl)hexyloxy)-5-hexyloxy-1,4- Dibromobenzene

2-(6'-(4'-amino-1',8'-naphthalimide-9'-alkyl)hexyloxy)-5-hexyloxy-1,4-dibromobenzene (0.618g , 1.0mmol), iodobenzene (1.020g, 5.0mmol), potassium carbonate (0.414g, 3.0mmol), 18-crown-6 (0.015g, 0.05mmol), cuprous iodide (0.0095g, 0.05mmol), DMPU 0.30mL was heated to 190°C under nitrogen protection for 48 hours. After extraction with chloroform, it was repeatedly washed, dried, filtered, and the product was separated by column chromatography to obtain 0.45 g of a red solid with a yield of 57%.

Example 25: 1,4-dibromo-2-hexyloxy-5-(6-(4-bis(4-iodophenyl-1-)amino-1,8-naphthalimide-9- )-hexyloxy)benzene

1,4-dibromo-2-hexyloxy-5-(6-(4-dianilino-1,8-naphthalimide-9-)-hexyloxy)benzene (3.99g, 5mmol) In 30ml of ethanol, add iodine (3.05g, 12mmol) in batches to the reaction flask under stirring at room temperature, then react for 30 minutes, pour the reaction mixture into water, extract with chloroform, wash with water, dry, and column separation to obtain 4.35g of orange-red solid , yield 82%.

Example 26: 1,4-Dibromo-2-hexyloxy-5-(6-(4-bis(4'-diphenylamino-biphenyl-4-)amino-1,8-naphthoylidene Amine-9-)-hexyloxy)benzene

1,4-Dibromo-2-hexyloxy-5-(6-(4-bis(4-iodophenyl-1-)amino-1,8-naphthalimide-9-)-hexyloxy Base) benzene (2.10g, 2mmol), triarylamine borate inanol ester (0.89, 2.4mmol), potassium fluoride (0.232g, 4mmol), tetrakis (triphenylphosphine) palladium (23mg, 0.02mmol), The mixture of 10 mL of DMP and 2 mL of water was heated to 100° C. for 6 hours under the protection of nitrogen, extracted with chloroform, washed with water, dried, and separated by column to obtain 2.31 g of red solid with a yield of 90%.

Example 27: 1,4-dibromo-2-hexyloxy-5-(6-(4-bis(4-formylphenyl-1-)amino-1,8-naphthalimide-9 -)-Hexyloxy)benzene

1,4-Dibromo-2-hexyloxy-5-(6-(4-bis(4-iodophenyl-1-)amino-1,8-naphthalimide-9-)-hexyloxy Base) benzene (3.20g, 4mmol) was dissolved in 20ml of DMF, phosphorus oxychloride (1.38g, 9mmol) was added, then heated to 120 ° C for 10 hours, the product was extracted with chloroform, washed with water, dried, and separated by column to obtain Orange-red solid 1.81g, yield 53%.

Example 28: 1,4-dibromo-2-hexyloxy-5-(6-(4-bis(4-styrylphenyl-1-)amino-1,8-naphthalimide- 9-)-Hexyloxy)benzene

1,4-Dibromo-2-hexyloxy-5-(6-(4-bis(4-formylphenyl-1-)amino-1,8-naphthalimide-9-)-hexyl A mixture of oxy)benzene (1.71g, 2mmol), tributylphosphinomethylenebenzene bromide (1.69g, 4.5mmol), sodium (0.192g, 8mmol), ethanol 10ml, and chloroform 10ml was stirred at room temperature for 3 hours. It was extracted with chloroform, washed with water, dried, and separated by a column to obtain 1.30 g of an orange-red solid with a yield of 65%.

Example 29: Synthesis of 4-N-(4-formylphenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide

Under the condition of ice-salt bath, POCl ₃ (15.40 g, 100 mmol) was added dropwise into DMF (7.30 g, 100 mmol), and stirred under N ₂ protection for 30 minutes. Then a DMF solution of 4-N, N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (3.30 g, 6.65 mmol) was added dropwise, and the temperature was gradually raised to 50° C., React for 20 hours. Washed with water, extracted with dichloromethane, washed repeatedly, dried, filtered, and separated by column chromatography to obtain 2.41 g of the product with a yield of 69%.

Example 30: 4-N-(4-(4'-bromostyryl)phenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthoylidene Amine Synthesis

4-N-(4-formylphenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.20g, 0.38mmol), 4 -Bromo-tributylphosphinomethylenebenzene bromide (0.17g, 0.38mmol) was dissolved in chloroform (8ml), then a solution of sodium metal (0.030g, 1.30mmol) in ethanol (3ml) was added dropwise, and reacted at room temperature for 10 Hour. The reaction was terminated by adding dilute hydrochloric acid solution, extracted with chloroform, washed repeatedly, dried, filtered, and separated by column chromatography to obtain 0.19 g of the product with a yield of 74%.

Example 31: Synthesis of 4-N-(4-methylphenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide

Under nitrogen protection, 4-bromo-9-(4-tert-butylphenyl)-1,8-naphthoimide (5.00g, 12.30mmol), 4-methyldianiline (2.47g, 13.50mmol ), anhydrous potassium carbonate (1.86g, 13.50mmol), cuprous iodide (0.24g, 1.23mmol), and 18-crown-6 (0.31g, 1.23mmol) were dissolved in 3 ml of DMPU solvent. React at 190° C. for 20 hours under magnetic stirring. The product was extracted with dichloromethane, washed with acid, washed with ammonia water, washed with water several times, and separated by column chromatography to obtain a pure intermediate product 4-N-(4-methylphenyl)-4-N-phenyl-9-(4- 1.87 g of tert-butylphenyl)-1,8-naphthalimide, orange-red solid, yield 30%.

Example 32: Preparation of 4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide synthesis

4-N-(4-methylphenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.54g, 1.06mmol), four Butyltribromide (1.02g, 2.12mmol) was dissolved in 10 ml of dichloromethane, reacted at room temperature for 1200 minutes, poured into water, washed the organic layer several times, and separated the product by column chromatography to obtain the pure product 4-N-( 4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide 0.61g, orange-red solid, yield 98 %.

Example 33: 4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-phenylamino)phenyl-9-(4-tert-butylphenyl)- Synthesis of 1,8-naphthalimide

Under nitrogen protection, add 4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8 - Naphthalimide (0.59g, 1.0mmol), 4-methyl-4'-trimethylene borate-triphenylamine (0.75g, 2.2mmol), anhydrous potassium carbonate (1.78g, 1.0mmol) , a mixture of toluene (10ml), water (10ml) and palladium catalyst (30mg) was reacted at 80° C. for 48 hours under magnetic stirring. Dichloromethane extraction, washing with water, drying, column separation, the product 4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-phenylamino)phenyl-9- (4-tert-butylphenyl)-1,8-naphthalimide, 0.50 g of red solid, yield 65%.

Example 34: 4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-bromophenylamino)phenyl-9-(4-tert-butylphenyl) -Synthesis of 1,8-naphthalimide

4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-phenylamino)phenyl-9-(4-tert-butylphenyl)-1,8 - Naphthalimide (0.77g, 1.0mmol), tetrabutylammonium tribromide (0.49g, 1.0mmol) were dissolved in 10 ml of dichloromethane, reacted at room temperature for 10 minutes, poured into water, and washed the organic layer several times , the product was separated by column chromatography to obtain the pure product 4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-bromophenylamino)phenyl-9-(4-tert 0.83 g of butylphenyl)-1,8-naphthalimide, orange-red solid, yield 98%.

Example 35: Synthesis of 4-N-(4-formylphenyl)-4-N-p-bromophenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide

4-N-(4-formylphenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.52g, 1.0mmol), four Butyl tribromide (0.52g, 1.07mmol) was dissolved in 10 ml of dichloromethane, reacted at room temperature for 20 minutes, poured into water, washed the organic layer several times, and separated the product by column chromatography to obtain the pure product 4-N-( 0.59 g of 4-formylphenyl)-4-N-bromophenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide, an orange-yellow solid, with a yield of 98%.

Example 36: Synthesis of 4-N-p-bromophenyl-4-N-(4-styryl)phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide

4-N-(4-formylphenyl)-4-N-bromophenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.48g, 0.80mmol), Tributylphosphinemethylenebenzene chloride (0.29g, 0.88mmol) was dissolved in chloroform (15ml), then a solution of sodium metal (0.055g, 2.40mmol) in ethanol (3ml) was added dropwise, and reacted at room temperature for 10 hours. Add dilute hydrochloric acid solution to terminate the reaction, extract with chloroform, wash with water, dry, and separate the product by column to obtain the product 4-N-bromophenyl-4-N-(4-styryl)phenyl-9-(4-tert-butyl 0.38 g of phenyl)-1,8-naphthalimide, orange-red solid, yield 72%.

Example 37: Synthesis and characterization of polymer luminescent material P1

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.56g, 2.0mmol), 2,2'-bipyridine (0.22g, 2.0mmol), 1,5-cyclooctadiene (0.32g , 2.0mmol) and DMF (5ml) were reacted at 80°C for half an hour, then 9.9'-dioctyl-2,7-dibromofluorene (0.4932g, 0.90mmol) and 4- N,N-di(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.066g, 0.10mmol) in toluene solution (5ml), reacted at 100°C After five days, it was poured into a mixture of methanol (100ml)/acetone (100ml)/concentrated hydrochloric acid (100ml) and stirred for two hours. After filtration, it was settled three times with methanol. The product was placed in a Soxhlet extractor and extracted with acetone for one day. The product was dried in vacuo to give an orange-yellow solid (0.24 g), yield 59%. The properties of the product are as follows: the number-average molecular weight is 12,000, the maximum ultraviolet absorption of the film is 380nm, and the solid-state fluorescence emission is 576nm.

The assembly conditions of single-layer devices (device structure: ITO/PEDOT/Polymer/Ca/Al) are as follows: use pre-cleaned ITO glass as the anode, and then spin-coat a layer of conductive polymer-polythiophene derivatives (PEDOT) (40nm ). After the PEDOT-modified ITO was vacuum-dried at 110° C. for 1 hour, a chloroform solution with a concentration of 10 mg/ml polymer was spin-coated on the ITO surface at a speed of 1500 rpm. Subsequently, 10 nm of metallic calcium and 100 nm of metallic aluminum were evaporated under high vacuum conditions. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.8 volts, the maximum brightness is 2870 cd/m ² , the maximum electroluminescent efficiency is 0.8 cd/A, and the color coordinates are (0.54, 0.35).

Example 38: Synthesis and characterization of polymer luminescent material P2

Under nitrogen protection, di-1,5-cyclooctadiene nickel (0.84g, 3.00mmol), 2,2'-bipyridine (0.33g, 3.0mmol), 1,5-cyclooctadiene (0.48g , 3.00mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.543g, 0.990mmol) and 4-N,N-bis(4-bromophenyl)-9-(4-tert Butylphenyl)-1,8-naphthalimide (0.0067g, 0.010mmol) in toluene (5ml) was reacted at 50°C for three days. All the other conditions and processing steps are the same as in Example 37. The product was an orange-yellow solid (0.25 g), yield 64%. The properties of the product are as follows: the number average molecular weight is 20,000, the maximum ultraviolet absorption of the solid is 382nm, and the fluorescence emission of the solid is 425, 448, and 550nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 6.6 volts, the maximum brightness is 10500 cd/m ² , the maximum electroluminescent efficiency is 2.8 cd/A, and the color coordinates are (0.34, 0.48) .

Example 39: Synthesis and characterization of polymer luminescent material P3

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for 1 hour. Then, 9.9'-dioctyl-2,7-dibromofluorene (0.545 g, 0.995 mmol) and 4-N, N-bis(4-bromophenyl)-9-(4- tert-Butylphenyl)-1,8-naphthoimide (0.0033g, 0.0050mmol) in toluene (5ml) was reacted at 80°C for one day. All the other conditions and processing steps are the same as in Example 37. The product was an orange-yellow solid (0.28 g), yield 72%. The properties of the product are as follows: the number average molecular weight is 17,000, the maximum ultraviolet absorption of the solid is 380nm, and the fluorescence emission of the solid is 438, 461, and 550nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.8 volts, the maximum brightness is 18300 cd/m ² , the maximum electroluminescence efficiency is 3.8 cd/A, and the color coordinates are (0.29, 0.45) .

Example 40: Synthesis and characterization of polymer luminescent material P4

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for 1 hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.546g, 0.997mmol) and 4-N,N-bis(4-bromophenyl)-9-(4-tert Butylphenyl)-1,8-naphthalimide (0.0020g, 0.0030mmol) in toluene (5ml) was reacted at 80°C for two days. All the other conditions and processing steps are the same as in Example 37. The product was an orange-yellow solid (0.27 g), yield 70%. The properties of the product are as follows: the number average molecular weight is 19,000, the maximum ultraviolet absorption of the solid is 382nm, and the fluorescence emission of the solid is 426, 444, and 542nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.4 volts, the maximum brightness is 12900 cd/m ² , the maximum electroluminescent efficiency is 4.2 cd/A, and the color coordinates are (0.29, 0.45) .

Example 41: Synthesis and characterization of polymer luminescent material P5

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 85°C for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.548g, 0.9995mmol) and 4-N,N-di(4-bromophenyl)-9-(4-tert Butylphenyl)-1,8-naphthalimide (0.00033g, 0.00050mmol) in toluene (5ml) was reacted at 80°C for one day. All the other conditions and processing steps are the same as in Example 37. The product was a light yellow solid (0.30 g), yield 77%. The properties of the product are as follows: the number average molecular weight is 30,000, the maximum ultraviolet absorption of the solid is 384nm, and the fluorescence emission of the solid is 433, 447, and 540nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 4.8 volts, the maximum brightness is 8820 cd/m ² , the maximum electroluminescence efficiency is 3.9 cd/A, and the color coordinates of the white light device are (0.30 , 0.40).

Example 42: Synthesis and characterization of polymer luminescent material P6

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then add 9.9'-bis(4-octyloxy)phenyl-2,7-dibromofluorene (0.5088g, 0.695mmol), 9,9-bis(10'-(p-(5 "-Phenyl-1", 3", 4"-oxadiazole-2"-)phenoxy)decyloxy)-2,7-dibromofluorene (0.3228g, 0.30mmol) and 4-N , N-bis(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.0033g, 0.0050mmol) in toluene solution (5ml), 85°C for four Day.All the other conditions and processing steps are the same as in Example 37.The product is orange-yellow solid 0.31g, yield 46%.Product properties are as follows: the number average molecular weight is 22,000, and the solid ultraviolet maximum absorption is 382nm, and the solid fluorescence emission is 421,447, 558nm..

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.8 volts, the maximum brightness is 9330 cd/m ² , the maximum electroluminescence efficiency is 1.8 cd/A, and the color coordinates of the white light device are (0.30, 0.46).

Example 43: Synthesis and characterization of polymer luminescent material P7

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for 1 hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.545g, 0.995mmol) and 4-N,N-bis(4-bromostyryl)phenyl)-9- (4-tert-butylphenyl)-1,8-naphthalimide (0.0043g, 0.0050mmol) in toluene (5ml) was reacted at 80°C for five days. All the other conditions and processing steps are the same as in Example 37. The product was an orange-yellow solid (0.25 g), yield 64%. The properties of the product are as follows: the number average molecular weight is 22,000, the maximum ultraviolet absorption of the solid is 382nm, and the fluorescence emission of the solid is 435, 451, and 551nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 4.8 volts, the maximum brightness is 12400 cd/m ² , the maximum electroluminescent efficiency is 2.7 cd/A, and the color coordinates of the white light device are (0.29, 0.33).

Example 44: Synthesis and characterization of polymer luminescent material P8

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.493g, 0.899mmol), N,N'-bis(4-methyl-phenyl)-N,N'- Bis(4-bromophenyl)-1,4-phenylenediamine (0.0672g, 0.10mmol) and 4-N,N-(4,4'-bis-(4-p-tolyl-4-bromophenyl -Amino)phenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.0058g, 0.0001mmol) in toluene (5ml) was reacted at 80°C for three days. All the other conditions and processing steps are the same as in Example 37. The product was an orange-yellow solid (0.30 g), with a yield of 75%. The properties of the product were as follows: the number average molecular weight was 35,000, the maximum ultraviolet absorption of the solid was 382 nm, and the fluorescence emission of the solid was 428, 450, and 552 nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.4 volts, the maximum brightness is 8880 cd/m ² , the maximum electroluminescent efficiency is 1.8 cd/A, and the color coordinate of the white light device is (0.25, 0.34).

Example 45: Synthesis and characterization of polymer luminescent material P9

Under the protection of nitrogen, 2,7-dibromo-9,9-dioctylfluorene (0.2713g, 0.495mmol), 2,7-bis(trimethylene borate)-9 were added to the reaction flask, 9-Dioctylfluorene (0.2792g, 0.50mmol) and 4-N,N-(4,4'-bis-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9- (4-tert-butylphenyl)-1,8-naphthalimide (0.00012g, 0.0001mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis (triphenylphosphine) palladium (0.0060g, 0.0005mmol), then toluene (4ml) and water (1.5ml) were added. After reacting at 100°C for 24 hours, the reaction mixture was poured into methanol to obtain a black solid, which was filtered, dissolved in chloroform, washed several times with water, dried over anhydrous _Na2SO4 , concentrated, settled in methanol three times, and extracted with acetone for 24 hours , a bright yellow solid (0.26 g) was obtained with a yield of 65%. The properties of the product are as follows: the number average molecular weight is 30,600, the maximum ultraviolet absorption of the solid is 382nm, and the fluorescence emission of the solid is 424, 442, and 550nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.2 volts, the maximum brightness is 7950 cd/m ² , the maximum electroluminescent efficiency is 2.0 cd/A, and the color coordinates of the white light device are (0.24, 0.31).

Example 46: Synthesis and characterization of polymer luminescent material P10

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.1096g, 0.195mmol), 2,7-bis(trimethylene borate)-9 was added to the reaction flask, 9-Dioctylfluorene (0.2792g, 0.50mmol), N,N'-bis(4-methyl-phenyl)-N,N'-bis(4-bromophenyl)-1,4-benzenedi Amine (0.2016g, 0.30mmol) and 4-N,N-(4,4'-bis-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9-(4-tert-butyl phenyl)-1,8-naphthalimide (0.0058g, 0.0050mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis (triphenylphosphine) palladium (0.0060g, 0.0005mmol), and Toluene (4ml) and water (1.5ml) were added. After reacting at 50°C for 120 hours, other conditions and treatment steps were the same as in Example 45. A bright yellow solid (0.26 g) was obtained in 65% yield. The properties of the product are as follows: the number-average molecular weight is 30,600, the maximum ultraviolet absorption of the solid is 382nm, and the fluorescence emission of the solid is 424, 442, and 561nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.2 volts, the maximum brightness is 7950 cd/m ² , the maximum electroluminescence efficiency is 2.0 cd/A, and the color coordinates of the white light device are (0.34, 0.39).

Example 47: Synthesis and characterization of polymer luminescent material P11

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.2166g, 0.40mmol), 2,7-bis(trimethylene borate)-9 were added to the reaction flask, 9-Dioctylfluorene (0.2792g, 0.50mmol) and 4-N,N-(4,4'-bis-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9- (4-tert-butylphenyl)-1,8-naphthalimide (0.116g, 0.10mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis (triphenylphosphine) palladium (0.0060g, 0.0005mmol), then toluene (4ml) and water (1.5ml) were added. After reacting at 85°C for 48 hours, the remaining conditions and treatment steps were the same as in Example 45. A bright yellow solid (0.26 g) was obtained in 65% yield. The properties of the product are as follows: the number average molecular weight is 30,600, the maximum ultraviolet absorption of the solid is 382nm, and the fluorescence emission of the solid is 581nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.2 volts, the maximum brightness is 1950 cd/m ² , the maximum electroluminescence efficiency is 1.0 cd/A, and the device color coordinates are (0.60, 0.36 ).

Example 48: Synthesis and characterization of polymer luminescent material P12

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.548g, 0.9995mmol) and 4-N,N-(4,4'-bis-(4-p-tolyl- 4-bromophenyl-amino)carbazolyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.0006g, 0.0005mmol) in toluene (5ml), 85°C Respond for five days. All the other conditions and processing steps are the same as in Example 37. The product was a yellow solid (0.22g), 57% yield. The properties of the product are as follows: the number-average molecular weight is 21,200, the maximum ultraviolet absorption of the solid is 385nm, and the fluorescence emission of the solid is 428, 442, and 525nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.0 volts, the maximum brightness is 6550 cd/m ² , the maximum electroluminescent efficiency is 2.1 cd/A, and the color coordinates of the white light device are (0.35, 0.40).

Example 49: Synthesis and characterization of polymer luminescent material P13

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then 9.9'-dioctyl-2,7-dibromofluorene (0.545 g, 0.995 mmol) and 9-phenyl-9-((4-N-(4-(4'-benzene Vinyl)phenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthoimide)-2,7-dibromofluorene (0.0050g, 0.0049 mmol) in toluene solution (5ml), reacted for five days at 80°C. All the other conditions and processing steps were the same as in Example 37. The product was a yellow solid (0.24g), and the yield was 62%. The product properties were as follows: the number average molecular weight was 27,000, solid The maximum ultraviolet absorption is 385nm, and the solid fluorescence emission is 428, 442, 532nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.8 volts, the maximum brightness is 9050 cd/m ² , the maximum electroluminescent efficiency is 2.8 cd/A, and the color coordinate of the white light device is (0.27, 0.32).

Example 50: Synthesis and characterization of polymer luminescent material P14

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.10696g, 0.1395mmol), 2,7-bis(trimethylene borate)-9, 9-Dioctylfluorene (0.2792g, 0.5mmol), N,N'-bis(4-methyl-phenyl)-N,N'-bis(4-bromophenyl)-1,4-benzenedi Amine (0.2016g, 0.30mmol), 9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-phenyl-9-(4-tert Butylphenyl)-1,8-naphthoimido)-2,7-dibromofluorene (0.0050g, 0.0050mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis(triphenylphosphine ) and palladium (0.0060g, 0.0005mmol), then add toluene (5ml) and water (2.0ml). 50 ℃ of reaction 120 hours. All the other conditions and processing steps are the same as embodiment 45, obtain bright yellow solid (0.25g), produce The yield is 65%. The properties of the product are as follows: the number average molecular weight is 25,600, the maximum solid ultraviolet absorption is 382nm, and the solid fluorescence emission is 424,442,531nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.6 volts, the maximum brightness is 9970 cd/m ² , the maximum electroluminescent efficiency is 1.7 cd/A, and the color coordinates of white light are (0.26, 0.33 ).

Example 51: Synthesis and characterization of polymer luminescent material P15

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.2739g, 0.4999mmol), 2,7-bis(trimethylene borate group)-9 was added to the reaction flask, 9-dioctylfluorene (0.2792g, 0.5mmol), 2-(6'-(4'-N,N-diphenylamino-1',8'-naphthalimide-9'-alkyl) Hexyloxy)-5-hexyloxy-1,4-dibromobenzene (0.00081g, 0.0001mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis(triphenylphosphine) palladium (0.0060g, 0.0005mmol), then added toluene (4ml) and water (3ml), and reacted at 100°C for 24 hours. The remaining conditions and processing steps were the same as in Example 45 to obtain a bright yellow solid (0.21g), with a yield of 54%. The properties of the product are as follows: the number average molecular weight is 23,000, the maximum ultraviolet absorption of the solid is 378nm, and the fluorescence emission of the solid is 435,510nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.8 volts, the maximum brightness is 13080 cd/m ² , the maximum electroluminescence efficiency is 6.6 cd/A, and the color coordinates are (0.13, 0.50) .

Example 52: Synthesis and characterization of polymer luminescent material P16

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.56g, 2.0mmol), 2,2'-bipyridine (0.22g, 2.0mmol), 1,5-cyclooctadiene (0.32g , 2.0 mmol) and DMF (5 ml) were reacted at 80° C. for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.3288g, 0.60mmol), 2-(6'-(4'-N,N-diphenylamino-1' , 8'-naphthalimide-9'-alkyl)hexyloxy)-5-hexyloxy-1,4-dibromobenzene (0.08g, 0.1mmol) and N,N'-bis(4- Methyl-phenyl)-N,N'-bis(4-bromophenyl)-1,4-phenylenediamine (0.20162g, 0.30mmol) in toluene (5ml) was reacted at 100°C for one day. All the other conditions and processing steps are the same as in Example 37. The product was a yellow solid (0.24g), 60% yield. The properties of the product are as follows: the number average molecular weight is 26,000, the maximum ultraviolet absorption of the solid is 375nm, and the fluorescence emission of the solid is 519nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.2 volts, the maximum brightness is 8450 cd/m ² , the maximum electroluminescence efficiency is 1.2 cd/A, and the color coordinates are (0.26, 0.68) .

Example 53: Synthesis and characterization of polymer luminescent material P17

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.844g, 3.0mmol), 2,2'-bipyridine (0.33g, 3.0mmol), 1,5-cyclooctadiene (0.48g , 3.0 mmol) and DMF (5 ml) were reacted at 80° C. for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.548g, 0.9999mmol) and 1,4-dibromo-2-hexyloxy-5-(6-(4- Bis(4'-dianilino-biphenyl-4-)amino-1,8-naphthoimide-9-)-hexyloxy)benzene (0.13g, 0.0001mmol) in toluene (5ml), React at 50°C for five days. All the other conditions and processing steps are the same as in Example 37. The product was an orange solid (0.24g), 60% yield. The properties of the product are as follows: the number average molecular weight is 24,800, the maximum ultraviolet absorption of the solid is 375nm, and the fluorescence emission of the solid is 435,551nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.0 volts, the maximum brightness is 15400 cd/m ² , the maximum electroluminescence efficiency is 4.2 cd/A, and the color coordinates of white light are (0.27, 0.34 ).

Example 54: Synthesis and characterization of polymer luminescent material P18

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then 9.9'-dioctyl-2,7-dibromofluorene (0.54534 g, 0.995 mmol) and 1,4-dibromo-2-hexyloxy-5-(6-(4- Bis(4-styrylphenyl-1-)amino-1,8-naphthalimide-9-)-hexyloxy)benzene (0.0050g, 0.005mmol) in toluene solution (5ml), 80°C Response for three days. All the other conditions and processing steps are the same as in Example 37. The product was an orange solid (0.24g), 60% yield. The properties of the product are as follows: the number average molecular weight is 24,800, the maximum ultraviolet absorption of the solid is 375nm, and the fluorescence emission of the solid is 440,552nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 4.8 volts, the maximum brightness is 12400 cd/m ² , the maximum electroluminescent efficiency is 2.2 cd/A, and the color coordinates of white light are (0.30, 0.34 ).

Example 55: Synthesis and characterization of polymer luminescent material P19

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.844g, 3.0mmol), 2,2'-bipyridine (0.33g, 3.0mmol), 1,5-cyclooctadiene (0.48g , 3.0 mmol) and DMF (5 ml) were reacted at 80° C. for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.545g, 0.995mmol) in toluene solution (5ml) to the reaction flask, after reacting for one day at 100°C, add and 4-N-(4- (4'-bromostyryl)phenyl)-4-N-phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.0034g, 0.0050mmol) in toluene (0.5ml), the reaction was continued at 80°C for one hour. All the other conditions and processing steps are the same as in Example 37. The product was a yellow solid (0.28g), 72% yield. The properties of the product are as follows: the number average molecular weight is 19,600. , the solid ultraviolet absorption maximum is 383nm, and the solid fluorescence emission is 425, 447, 528nm..

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.2 volts, the maximum brightness is 16880 cd/m ² , the maximum electroluminescent efficiency is 2.6 cd/A, and the color coordinates of the white light device are (0.25, 0.38).

Example 56: Synthesis and characterization of polymer luminescent material P20

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.56g, 2.0mmol), 2,2'-bipyridine (0.22g, 2.0mmol), 1,5-cyclooctadiene (0.32g , 2.0 mmol) and DMF (5 ml) were reacted at 80° C. for half an hour. Then, a toluene solution (5ml) of 9.9'-dioctyl-2,7-dibromofluorene (0.545g, 0.995mmol) was added to the reaction flask, and after five days of reaction at 50°C, 4-N-(4-methyl phenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.0029g, 0.0049mmol) in toluene (0.5ml ), after continuing to react for two days at 50°C. All the other conditions and processing steps are the same as in Example 37. The product was a yellow solid (0.27g), 70% yield. The properties of the product are as follows: the number average molecular weight is 22,450, the maximum ultraviolet absorption of the solid is 380nm, and the fluorescence emission of the solid is 430, 451, and 523nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 6.8 volts, the maximum brightness is 19280 cd/m ² , the maximum electroluminescence efficiency is 7.4 cd/A, and the color coordinates are (0.34, 0.50) .

Example 57: Synthesis and characterization of polymer luminescent material P21

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.2714g, 0.495mmol), 2,7-bis(trimethylene borate)-9 were added to the reaction flask, 9-dioctylfluorene (0.2792g, 0.5mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis (triphenylphosphine) palladium (0.0060g, 0.0005mmol), then add toluene (4ml) and water (1.5ml). After reacting at 100°C for 24 hours, add 4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthoyl After the imine (0.0029g, 0.005mmol), the reaction was continued at 100°C for 1 hour. The remaining conditions and treatment steps were the same as in Example 45, and a bright yellow solid (0.21g) was obtained with a yield of 54%. The properties of the product are as follows: the number-average molecular weight is 20,300, the maximum ultraviolet absorption of the solid is 387nm, and the fluorescence emission of the solid is 435, 443, and 525nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 6.4 volts, the maximum brightness is 17780 cd/m ² , the maximum electroluminescent efficiency is 7.2 cd/A, and the color coordinates are (0.34, 0.52) .

Example 58: Synthesis and characterization of polymer luminescent material P22

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.1096g, 0.1999mmol), 2,7-bis(trimethylene borate)-9, 9-Dioctylfluorene (0.2792g, 0.5mmol), N,N'-bis(4-methyl-phenyl)-N,N'-bis(4-bromophenyl)-1,4-benzenedi Amine (0.2016g, 0.30mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis(triphenylphosphine)palladium (0.0060g, 0.0005mmol), then toluene (4ml) and water (1.5ml) were added. After reacting at 50°C for 120 hours, add 4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthoyl After the imine (0.00058g, 0.0001mmol), the reaction was continued at 50°C for 48 hours. The other conditions and treatment steps were the same as in Example 45, and a bright yellow solid (0.26g) was obtained with a yield of 59%. The properties of the product are as follows: the number average molecular weight is 23,400, the maximum ultraviolet absorption of the solid is 385nm, and the fluorescence emission of the solid is 435, 443, and 520nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.2 volts, the maximum brightness is 7980 cd/m ² , the maximum electroluminescent efficiency is 2.2 cd/A, and the color coordinates are (0.23, 0.28) .

Example 59: Synthesis and characterization of polymer luminescent material P23

Under nitrogen protection, 2,7-dibromo-9,9-dioctylfluorene (0.2192g, 0.40mmol), 2,7-bis(trimethylene borate)-9 were added to the reaction flask, 9-dioctylfluorene (0.2792g, 0.5mmol), anhydrous potassium carbonate (0.4140g, 3mmol), tetrakis (triphenylphosphine) palladium (0.0060g, 0.0005mmol), then add toluene (4ml) and water (1.5ml). After reacting at 50°C for 120 hours, add 4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthoyl After the imine (0.058g, 0.10mmol), the reaction was continued at 50°C for 48 hours. The remaining conditions and treatment steps were the same as in Example 45, and a bright yellow solid (0.21g) was obtained with a yield of 53%. The properties of the product are as follows: the number average molecular weight is 7,400, the maximum ultraviolet absorption of the solid is 380nm, and the fluorescence emission of the solid is 535nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.4 volts, the maximum brightness is 1770cd/m ² , the maximum electroluminescent efficiency is 0.82cd/A, and the color coordinates are (0.40, 0.58) .

Example 60: Synthesis and characterization of polymer luminescent material P24

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.3835g, 0.6999mmol) and N,N'-bis(4-methyl-phenyl)-N,N'- Bis(4-bromophenyl)-1,4-phenylenediamine (0.2016g, 0.30mmol) in toluene (5ml), reacted at 80°C for three days, added 4-N-(4-methylphenyl)- 4-N-(4-bromophenyl)-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.00058g, 0.0001mmol) in toluene (0.5ml), continued at 80°C After a day of reaction. All the other conditions and processing steps are the same as in Example 37. The product was a yellow solid (0.27g), 47% yield. The properties of the product were as follows: the number average molecular weight was 26,700. The maximum ultraviolet absorption of the solid is 380nm, and the fluorescence emission of the solid is 430, 441, 525nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 6.0 volts, the maximum brightness is 4350 cd/m ² , the maximum electroluminescence efficiency is 1.8 cd/A, and the color coordinates are (0.23, 0.21) .

Example 61: Synthesis and characterization of polymer luminescent material P25

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then, a toluene solution (5ml) of 9.9'-dioctyl-2,7-dibromofluorene (0.5453g, 0.995mmol) was added to the reaction flask, and after three days of reaction at 80°C, 4-N-(4-methyl phenyl)-4-N-(4-tolyl-4'-bromophenylamino)phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.0042g , 0.005mmol) in toluene solution (0.5ml), continue to react at 80°C for one day, and the post-treatment steps are the same as in Example 37. The product was a yellow solid (0.25g), 64% yield. The properties of the product were as follows: the number average molecular weight was 20,700. The maximum ultraviolet absorption of the solid is 381nm, and the fluorescence emission of the solid is 433, 545nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 6.0 volts, the maximum brightness is 10950 cd/m ² , the maximum electroluminescent efficiency is 4.3 cd/A, and the color coordinates of the white light device are (0.28, 0.32).

Example 62: Synthesis and characterization of polymer luminescent material P26

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then, a toluene solution (5ml) of 9.9'-dioctyl-2,7-dibromofluorene (0.4932g, 0.90mmol) was added to the reaction flask, and after three days of reaction at 80°C, 4-N-(4-methyl phenyl)-4-N-(4-tolyl-4'-bromophenylamino)phenyl-9-(4-tert-butylphenyl)-1,8-naphthalimide (0.084g , 0.1 mmol) in toluene solution (0.5 ml), continue to react at 80 ° C for one day, and the post-treatment steps are the same as in Example 37. The product was a yellow solid (0.26 g), 60% yield. The properties of the product were as follows: the number average molecular weight was 6,700. The solid ultraviolet absorption maximum is 381nm, and the solid fluorescence emission is 553nm.

The single-layer device assembly conditions are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.4 volts, the maximum brightness is 2950 cd/m ² , the maximum electroluminescence efficiency is 1.3 cd/A, and the device color coordinates are (0.43, 0.56 ).

Example 63: Synthesis and characterization of polymer luminescent material P27

Under nitrogen protection, two-1,5-cyclooctadiene nickel (0.619g, 2.20mmol), 2,2'-bipyridine (0.24g, 2.2mmol), 1,5-cyclooctadiene (0.352g , 2.20mmol) and DMF (5ml) were reacted at 80°C for half an hour. Then add 9.9'-dioctyl-2,7-dibromofluorene (0.5453g, 0.995mmol) to the reaction flask, react at 80°C for three days, add 4-N-p-bromophenyl-4-N-( 4-Styryl)phenyl-9-(4-tert-butylphenyl)-1,8-naphthoimide (0.0034g, 0.005mmol) in toluene solution (0.5ml), continue to react at 80°C for one day, Post-processing steps are the same as in Example 37. The product was a yellow solid (0.22g), 57% yield. The properties of the product were as follows: the number average molecular weight was 19,200. The maximum ultraviolet absorption of the solid is 376nm, and the fluorescence emission of the solid is 433, 540nm.

The assembly conditions of the single-layer device are the same as in Example 37. The performance of the single-layer electroluminescent device is as follows: the starting voltage is 5.0 volts, the maximum brightness is 9940 cd/m ² , the maximum electroluminescence efficiency is 3.3 cd/A, and the color coordinates of the white light device are (0.27, 0.33).

Claims (2)

1. A white electroluminescent polymer material, characterized in that it has the following structure: End group type single white light polymer luminescent material:

Wherein: _R1 is independently selected from hexyl, octyl, phenyl, fluorenyl, or selected from hexyl substituted phenyl, hexyl substituted fluorenyl, octyl substituted phenyl or octyl substituted Fluorenyl; Ar1 is a naphthalimide derivative unit, selected from one or more of the following structural units: Wherein: _R3 is independently selected from methyl, butyl, hexyl, octyl, decyl or aryl; _R4 is independently selected from methyl, butyl or aryl; wherein aryl is independently selected from phenyl, Naphthyl, butyl or tert-butyl substituted phenyl or naphthyl; _R independently selected from hydrogen, methyl or methoxy; Ar2 is an electron transport unit or a hole transport unit, selected from one or more of the following structural units:

Wherein: R is _{independently} selected from methyl, butyl or tert-butyl; x and y are the content of each element, satisfying 0<x<1, 0<y<1, x+y=1, n is an integer greater than 1 and less than or equal to 300. 2. A method for preparing the white electroluminescent polymer material according to claim 1, comprising the preparation of (A) monomer and (B) polymer; (A) Preparation of monomer The preparation of monobromonaphthalimide derivative monomer, its structural general formula is: Where Ar1 is the same as Ar1 in the end-group single white light polymer material; The preparation method of monobromonaphthalimide derivative monomer is as follows: Dissolve the naphthalimide derivative Ar1H and tetrabutylammonium tribromide with a molar ratio of 1-2 times in dichloromethane, react at room temperature for 10-1200 minutes, pour the reaction product into water, separate the organic phase, repeat After washing several times with water, drying, concentrating, and recrystallizing, monobromonaphthalimide derivative monomers are obtained; (B) Preparation of polymer Preparation of terminal-type white light polymer materials The preparation of end-type white light polymer materials adopts Yamamoto and Suzuki polymerization, and its preparation method is as follows: Yamamoto polymerization reaction: under the protection of nitrogen, 2,7-dibromofluorene derivative monomer and 0%<molar ratio≤30% bibromoaromatic monomer Ar2 are dissolved in anhydrous toluene, and then added dropwise to In a DMF solution with a molar ratio of 2-3 times Ni(O), react at a temperature of 50-100° C. for 24-120 hours and then add 0.01%-10% molar ratio of monobromonaphthalimide derivative monomer, Continue to react at a temperature of 50-100°C for 1-48 hours, use a methanol/concentrated hydrochloric acid mixed solution to terminate the reaction, extract and separate, concentrate and precipitate, solvent extract, and vacuum dry to obtain a fibrous polymer luminescent material; Suzuki polymerization reaction: Dissolve 2,7-bisboronate fluorene derivative monomer and 0.0001%-30% molar ratio of bisbrominated aromatic monomer Ar2 in toluene, and then add 2.0M potassium carbonate with a molar ratio of 3 times solution, under nitrogen protection and a temperature of 50-100°C, add 0.050% molar ratio of tetrakis(triphenylphosphine) palladium, and add 0.01%-10% molar ratio of monobromonaphthoyl after reacting for 24-120 hours Amine derivative monomers, continue to react at 50-100°C for 1-48 hours, use 0.1M dilute hydrochloric acid solution to terminate the reaction, extract with chloroform, settle with methanol, extract with solvent, and dry in vacuum to obtain fibrous polymer materials .