White electroluminescent polymeric material and preparation thereof

This invention relates to a white electroluminescent polymeric material and preparation thereof. Based on the physical idea that white light emission can be achieved by regulating the relative luminous intensities of blue- and orange-light emitting units located in a single polymer molecule, the present invention provides three types (main chain type, pendant chain type, and terminal group type) of high efficiency and stable white electroluminescent polymeric material systems.

TECHNICAL FIELD

This invention relates to a white electroluminescent polymeric material and preparation thereof.

BACKGROUND ART

Since the electroluminescence of poly(p-phenylene vinylene) (PPV) was first reported by Burroughs et al, Cambridge Univ. U.K. in 1990, the polymeric electroluminescent material and manufacturing device thereof has been extensively concerned and investigated by the research and industry circles due to its prominent characteristics of simple process, easy to achieve large screen display and flexible display etc. At present, some typical blue-, green- and red-light polymeric luminescent material systems, such as poly(p-phenylene) (PPP), poly(alkylfluorene) (PAF), poly(phenylvinylene) (PPV), polythiophene (PTh) etc, have been developed. All the performance indexes of the monochromatic light polymeric electroluminescent device made of them can fulfill practical requirements. By contrast, there is a larger gap between every performance index of white light polymeric device and practical requirement. It is necessary to research deeply the material design and device structure separately so as to accelerate the course of industrialization of white light polymeric device.

The means for achieving white light polymeric electroluminescent device mainly include: (1) blending system of organic fluorescent dye/polymer; (2) blending system of polymer/polymer; (3) single white light polymeric system. For example, J. kido et al. disclosed a method for obtaining white luminescence with a maximum luminance of 3400 cd/m2by dispersing three kinds of fluorescent dyes (red, green and blue) in poly(vinylcarbazol) (PVK) and regulating the contents of the three dyes, Appl. Phys. Lett., 64, 815, 1994; Inganas et al. disclosed another method for obtaining a white light emission (CIE 0.220, 0.466) by blending the polythiophene derivatives (red, green and blue) with an inert polymer (such as PMMA) under a high driving voltage (20V), Appl. Phys. Lett., 68, 147, 1996. But the system has the following disadvantages: the obvious phase separation between polymer and polymer results in the voltage-dependence of white light emission, and thus a stable white light device is difficult to be obtained. Leising research group disclosed a method for obtaining a white light polymeric device having an external quantum efficiency of 1.2% by dispersing a trace amount (0.66 wt %) of red light poly(perylene-co-diethynylbenzene) (PPDB) in a high efficiency blue light laddertype (polyparaphenylene) (m-LPPP), in which the voltage-dependence of white color purity was improved to a certain extent due to the formation of a homogeneous blending system of polymer/polymer, see Appl. Phys. Lett., 71, 2883, 1997. For the single polymeric white light system disclosed in “Appl. Phys. Lett., 79, 308, 2001” and “Macromolecules, 35, 6782, 2002”, it is obtained by forming an exciplex during the electroluminescence of PPV polymer (blue or blue-green), which can bring about a wide-band luminescence, so the white light polymeric device made thereof has a sharp voltage-dependence of color and relatively poor performances.

DISCLOSURE OF THE INVENTION

The object of this invention is to provide a white electroluminescent polymeric material.

Another object of this invention is to provide a method for preparing a white electroluminescent polymeric material.

The inventors of the present invention find that white light emission can be achieved by regulating the relative luminous intensities of blue- and orange-light emitting units located in a single polymer molecule. Based on such a physical idea, the present invention provides three types (main chain type, pendant chain type, and terminal group type) of high efficiency and stable white electroluminescent polymeric material systems.

The present invention provides the following aspects.

1. A white electroluminescent polymeric material, which comprising a single white electroluminescent polymeric material selected from a group consisting of:

type (I): main chain type single white electroluminescent polymeric material,

wherein: R1is alkyl or aryl, Ar1 is a naphthalimide derivative basic unit having one or more structures as listed below:

wherein, Ar2 is an electron transport basic unit, a hole transport basic unit or a luminescence basic unit; x, y, and z each represents the content of one basic unit, satisfying 0<x<1, 0<y<1, 0≦z<1, x+y+z=1, and n=1-300, wherein, the chain lengths of the alkyl and the alkoxy are 1-18; the aryl is selected from a group consisting of phenyl, naphthyl, fluorenyl, triphenylamino, oxadizolyl, and phenyl or naphthyl substituted by alkyl or alkoxy; R3and R4independently represent an alkyl having a chain length of 1-18 or an aryl, wherein the aryl is selected from a group consisting of phenyl, naphthyl, and phenyl or naphthyl substituted by alkyl or alkoxy;

Ar2 has one or more structural units selected from the following units:

wherein R5is selected from a group consisting of alkyl, phenyl, naphthyl, and phenyl or naphthyl substituted by alkyl or alkoxy, m=0-20; wherein, the chain lengths of the alkyl and the alkoxy are 1-18;

type (II): pendant chain type single white electroluminescent polymeric material

wherein: R2is selected from a group consisting of alkyl, alkoxy, phenyl, and phenyl substituted by alkyl or alkoxy; Ar1 is a naphthalimide derivative basic unit; The basic structure of Ar2 is the same as the Ar2 of the main chain type single white luminescent polymeric material; Each basic unit content—x, y and z satisfy 0<x≦1, 0<y<1, 0≦z<1, x+y+z=1, m=0-20, n=1-300; wherein the chain lengths of the alkyl and the alkoxy are 1-18;

Ar1 has one or more structures as listed below:

wherein R6is alkyl, phenyl, naphthyl, a phenyl or naphthyl group substituted by alkyl or alkoxy, wherein the chain lengths of the alkyl and the alkoxy are 1-18; and

type (III): Terminal group type single white electroluminescent polymeric material

wherein: Ar1 is a naphthalimide derivative basic unit; the structure of Ar2 is the same as the Ar2 of the main chain type single white luminescent polymeric material; x and y are basic unit contents and satisfy 0<x≦1, 0<y<1, x+y=1; n=1-300;

Ar1 has one or more structures as listed below:

wherein R7is alkyl, phenyl, naphthyl, or a phenyl or naphthyl group substituted by alkyl or alkoxy; wherein the chain length of alkyl and alkoxy is 1-18.

2. A process for preparing the white electroluminescent polymeric material according to aspect 1, comprising steps of:a. providing a monomer selected from a group consisting of:(1) monomers with a formula as follows:

wherein, Ar1 is the same as that in the main chain type single white luminescent polymeric material according to aspect 1;(2) monomers with a formula as follows:

wherein, Ar1 is the same as that in the pendant chain type single white luminescent polymeric material according to aspect 1, m=0-20, preferably 1-20;(3) monomers with a formula as follows:

wherein, Ar1 is the same as that in the pendant chain type single white luminescent polymeric material according to aspect 1, m=0-20, preferably 1-20; and(4) monomers with a formula as follows:

wherein, Ar1 is the same as that in the pendant chain type single white luminescent polymeric material according to aspect 1, m=0-20, preferably 1-20;b. providing a monomer selected from a group consisting of:

wherein, Ar1 is the same as that in the terminal group type single white luminescent polymeric material defined in aspect 1; andc. polymerizing a monomer obtained in step (a) and a monomer obtained in step (b) using the Yamamoto polymerization method or the Suzuki polymerization method.

3. The method according to aspect 2, wherein the monomer (1) in step a is prepared by a method comprising steps of: dissolving naphthalimide derivative Ar1 and 2-4 mole equivalents of tetrabutyltriammonium bromide in dichloromethane; reacting the resulting solution, preferably at room temperature, for 10-1200 min; and separating the reaction product.

4. The method according to aspect 2, wherein the monomer (2) in step a is prepared by a method comprising steps of: dissolving 4-amino-1,8-naphthalimide and 1-5 mole equivalents of 2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene in dimethyl sulfoxide; adding 1-10 mole equivalents of MOH wherein M represents Li, Na or K; reacting at 50-150° C. for 1-120 hr; stopping the reaction and separating the intermediate product; dissolving the intermediate product, 2-20 mole equivalents of iodobenzene, 2-20 mole equivalents of carbonate, preferably, sodium carbonate or potassium carbonate, 1-5% mole equivalent of 18-crown-6 and 1-5% mole equivalent of cuprous iodide in a solvent, preferably DMPU (1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-primidinone); heating to 140-200° C. under an inert gas, preferably N2gas, to react for 5-50 hr; and separating the product.

5. The method according to aspect 2, wherein the monomer (3) in step a is prepared by a method comprising steps of: contacting N,N-diphenyl-1,8-naphthalimide derivative with 15-80 mole equivalents of POCl3in dimethyl formamide at 50˜100° C. for 20-100 hr to produce 4-aldo or 4,4′-dialdo-N,N-diphenyl-1,8-naphthalimide derivative; dissolving the resulting product and 0.5-1 mole equivalents of 9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene or 9,9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene in a chloroform solution; adding a solution of 4-10 mole equivalents of sodium ethoxide; reacting at room temperature for 10-50 hr; and separated the reaction product.

6. The method according to aspect 2, wherein the monomer (4) in step a is prepared by a method comprising the steps of: dissolving 9,9-(m-bromoalkyl)-2,7-dibromofluorene and 2-3 mole equivalents of 4-amino-1,8-naphthalimide in a solvent, preferably, DMSO; adding 2-20 mole equivalents of MOH wherein M represents Li, Na or K; reacting at 50-150° C. for 1-120 hr; separating the intermediate product; dissolving the intermediate product, 4-20 mole equivalents of iodobenzene, 6-20 mole equivalents of potassium carbonate, 2-10% mole equivalents of 18-crown-6, 2-10% mole equivalent of cuprous iodide in a solvent such as DMPU; heating the solution to 140-200° C. to react for 5-50 hr; and separated the product.

7. The method according to aspect 2, wherein the monomer b in step b is prepared using a method comprising steps of: dissolving naphthalimide derivative Ar1H and 1-2 mole equivalents of tetrabutyltriammonium bromide in a solvent, preferably, dichloromethane; reacting, preferably at room temperature, for 10-1200 min; and separated the product.

8. The method according to aspect 2, wherein, for obtaining the main chain type single white light polymeric material, the Yamamoto polymerization method comprising steps of:

dissolving 2,7-dibromofluorene derivative monomer, 0.01%-10% mole equivalent of dibromonaphthalimide derivative monomer and 0-30% mole equivalent of dibromoaromatic monomer in a solvent, preferably anhydrous toluene, under the protection of an inert gas, preferably N2gas;

dropping the resulting solution into a solution of 2-3 mole equivalents of Ni (0) in a solvent, preferably dimethyl formamide;

reacting at 50-100C. for 24-120 hr; and

separating the product.

9. The method according to aspect 2, wherein, for obtaining the main chain type single white light polymeric material, the Suzuki polymerization method comprising steps of:

dissolving 2,7-diborate fluorene derivative monomer, 0.01-10% mole equivalent of dibromonaphthalimide derivative monomer and 0-20% mole equivalent of dibromoaromatic monomer in a solvent, preferably toluene;

adding 3 mole equivalents of carbonate, preferably potassium carbonate or sodium carbonate, in a solution form;

under the protection of an inert gas, preferably N2gas and at 50-100° C., adding 0.05% mole equivalent of tetra(triphenylphosphino) palladium (0);

reacting for 1-200 hr; and

separating the product.

10. The method according to aspect 2, wherein, for obtaining the pendant chain type single white light polymeric material, the Yamamoto polymerization method comprising steps of:

dissolving 2,7-dibromofluorene derivative monomer, 0.01%-10% mole equivalent of any one of monomers (2)-(4) in step a, and 0-30% mole equivalent of dibromoaromatic monomer in a solvent, preferably anhydrous toluene, under the protection of an inert gas, preferably N2gas;

dropping the resulting solution into a solution of 2-3 mole equivalents of Ni (0) in a solvent, preferably dimethyl formamide;

reacting at 50-100° C. for 24-120 hr; and

separating the product.

11. The method according to aspect 2, wherein, for obtaining the pendant chain type single white light polymeric material, the Suzuki polymerization method comprising steps of:

dissolving 2,7-diborate fluorene derivative monomer, 0.01-10 mole equivalent of any one of monomers (2)-(4) in step a, and 0-20% mole equivalent of dibromoaromatic monomer in a solvent, preferably toluene;

adding 3 mole equivalents of carbonate, preferably potassium carbonate or sodium carbonate, in a solution form;

under the protection of an inert gas, preferably N2gas and at 50-100° C., adding 0.05% mole equivalent of tetra(triphenylphosphino) palladium (0);

reacting for 1-200 hr; and

separating the product.

12. The method according to aspect 2, wherein, for obtaining the terminal group type single white light polymeric material, the Yamamoto polymerization method comprising steps of:

dissolving 2,7-dibromofluorene derivative monomer and 0-30% mole equivalent of dibromoaromatic monomer in a solvent, preferably anhydrous toluene, under the protection of N2gas;

dropping the resulting solution into a solution of 2-3 mole equivalents of Ni (0) in a solvent, preferably dimethyl formamide;

reacting at 50-100° C. for 24-120 hr; and

separating the product.

13. The method according to aspect 2, wherein, for obtaining the terminal group type single white light polymeric material, the Suzuki polymerization method comprising steps of:

dissolving 2,7-diborate fluorene derivative monomer and 0-30% mole equivalent of dibromoaromatic monomer in a solvent, preferably toluene;

adding 3 mole equivalents of carbonate, preferably potassium carbonate or sodium carbonate, in a solution form;

under the protection of N2gas and at 50-100° C., adding 0.050% mole equivalent of tetra(triphenylphosphino) palladium (0);

adding 0.01-10% mole equivalent of monobromonaphthalimide derivative monomer;

reacting at 50-100° C. for 1-48 hr; and

separating the product.

PREFERRED EMBODIMENTS OF THE INVENTION

In this invention, polyfluorene and its derivative are used as the structural unit for blue light, naphthalimide derivative as that for orange light.

In the present invention, otherwise indicated, the term “alkyl” means a straight or branched alkyl having 1-18, preferably 1-10, more preferably 1-6 carbon atoms, the term “alkoxy group” means a straight or branched alkoxy group having 1-18, preferably 1-10, more preferably 1-6 carbon atoms, and the term “aryl” means an aryl optionally substituted by an alkyl or aryl, more preferably, having 6-18 carbon atoms.

The preparation methods for the three types of white electroluminescent polymeric material mainly relates to five types of monomers and two types of copolymerization reactions.

Examples of the preparations methods are provided as follows:

1. Preparation of 2,7-dibromofluorene and the Monomer Derived therefrom

The general structural formulas of 2,7-dibromofluorene and the monomer derived therefrom are as follows:

That is, 2,7-dibromofluorene and the monomer derived therefrom can be classified as 9,9-dialkyl-2,7-dibromofluorene monomer and 9,9-diaryl-2,7-dibromofluorene. Their preparation methods are respectively described as follows:

a) Preparation of 9,9-dialkyl-2,7-dibromofluorene monomer

2,7-dibromofluorene and 2-6 mole equivalents of excessive bromoalkane are dissolved in toluene, then 2-50 mole equivalents of 10-70% NaOH aqueous solution was added. After reacting under the protection of N2gas for 1-24 hr at 30-100° C., the reaction product was poured into water, and then the organic phase was separated, washed repeatedly with water, dried, concentrated and recrystallized to obtain 9,9-dialkyl-2,7-dibromofluorene.

b) Preparation of 9,9-diaryl-2,7-dibromofluorene monomer

First, 2,7-dibromofluorene ketone is dissolved in ethyl ether, under the protection of N2gas, 1-4 mole equivalents of an aryl Grignard reagent is then added. After reacting under reflux for 1-24 hr, 9-hydroxy-9-aryl-2,7-dibromofluorene is obtained. 9-hydroxy-9-aryl-2,7-dibromofluorene is then dropped slowly into an aryl hydrocarbon sulfuric acid solution in a mole ratio of 1:1-5. After refluxing for 1-24 hr, the reaction product is poured into water. The resulting organic phase is separated, washed repeatedly with water, dried, concentrated and recrystallized to obtain 9,9-diaryl-2,7-dibromofluorene.

2. Preparation of 9,9-disubstituted-2,7-biborate and Monomer Derived therefrom

The general structural formula of 9,9-disubstituted-2,7-biborate and monomer derived therefrom is one of the following formulas:

The preparation method for 9,9-dialkylfluorene-2,7-biborate, 9,9-spirobifluorene-2,7-biborate and monomer derived therefrom is as follows:

1-4 mole equivalents of n-butyllithium is added at −100˜0° C. into a solution of 2,7-dibromofluorene and monomer derived therefrom in THF. After stirring for 1-10 hr, 2-10 mole equivalents of trimethyl borate is then added at −100˜0° C. After stirring at room temperature for 1-48 hr, the reaction product is poured into water. Then the organic phase is separated, washed repeatedly with water, dried, concentrated, and dissolved in toluene. 2-10 mole equivalents of 1,3-propylene glycol is added. After refluxing for 1-72 hr, the reaction product is poured into water. The organic phase is separated, washed repeatedly with water, dried, concentrated and finally separated by column chromatography to produce 9,9-dialkylfluorene-2,7-biborate or 9,9-spirobifluorene-2,7-biborate and their derivatives.

3. Preparation of Dibromonaphthalimide Derivative Monomer

dibromonaphthalimide derivative monomer mainly includes: main chain type dibromonaphthalimide derivative monomers, pendant chain type dibromonaphthalimide derivative monomers and pendant chain type 9,9-disubstituted dibromofluorene naphthalimide derivative monomers;

1) The general structural formula of the main chain type dibromonaphthalimide derivative monomers is as follows:

wherein Ar1 is the same as the Ar1 in the main chain type single white light polymeric material.

The preparation method for the main chain type dibromonaphthalimide derivative monomers is as follows:

Naphthalimide derivative Ar1 and 2-10 mole equivalents of tetra-n-butylammonium tribromide are dissolved in dichloromethane. After reacting at 0-40° C. for 10-1200 min, the reaction product is poured into water, and the organic phase is separated, washed repeatedly with water, dried, concentrated and recrystallized to obtain a main chain type dibromonaphthalimide derivative monomer.

wherein Ar1 is the same as the Ar1 in the pendant chain type single white light polymeric material.

The preparation method for the pendant chain type dibromonaphthalimide derivative monomer is as follows:

First, 2-hydroxy-5-substituted-1,4-dibromobenzene and 1-3 mole equivalents of dibromoalkane with a chain segment number of m are dissolved in anhydrous ethanol, and refluxed in the presence of a solution of 1-10 mole equivalents of KOH for 2-10 hr to obtain 2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene as above. Naphthalimide derivative Ar1 and 1-5 mole equivalents of 2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene are dissolved in dimethyl sulfoxide. A solution of 1-10 mole equivalents of NaOH is added. After reacting at 20-150° C. for 1-5 days, the reaction is stopped with water. The organic phase is separated, washed repeatedly with water, dried, concentrated and separated by column chromatography to obtain a pendant chain type dibromonaphthalimide derivative monomer.

wherein Ar1 is the Ar1 in the pendant chain type single white light polymeric material.

(1) The preparation method for pendant chain type 9,9-dialkyl substituted dibromofluorene naphthalimide derivative monomer is as follows:

First, 2,7-dibromofluorene and 2-6 mole equivalents of dibromoalkane with a chain segment of (CH2)m are dissolved in toluene, and 10-70% aqueous solution of 2-50 mole equivalents of NaOH is then added. The reaction system reacted at 30-100° C. under the protection of N2gas for 1-24 hr to obtain 9,9-(m-bromoalkyl)-2,7-dibromofluorene with the above structure. Then, naphthalimide derivative Ar1 and 1-5 mole equivalents of 9,9-(m-bromoalkyl)-2,7-dibromofluorene are dissolved in DMSO. After adding a solution of 1-10 mole equivalents of NaOH and reacting at 20-150° C. for 1-5 days, the reaction is stopped with water, the organic phase is separated, washed repeatedly with water, dried, concentrated, and separated by column chromatography to obtain pendant chain type 9,9-dialkyl substituted dibromofluorene naphthalimide derivative monomer.

(2) The preparation method for the pendant chain type 9,9-diaryl substituted dibromofluorene naphthalimide derivative monomer is as follows:

First, N,N-diphenyl-1,8-naphthalimide derivative reacted with a solution of 2-40 mole equivalents of phosphorus oxychloride (POCl3) in dimethyl formamide (DMF) at −50˜0° C.(low-temperature) for 2-10 hr to produce 4-aldo or 4,4′-dialdo-N,N-diphenyl-1,8-naphthalimide derivative. Then, the resulting product and 1-4 mole equivalents of 9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene or 9,9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene are dissolved in a chloroform solution. And a solution of 1-10 mole equivalents of sodium ethoxide is then added. After reacting at 0-60° C. for 1-120 hr, the reaction product is poured into water, and the organic phase is separated, washed repeatedly with water, dried, concentrated, and finally separated by column chromatography to obtain pendant chain type 9,9-diaryl substituted dibromofluorene naphthalimide derivative monomer.

4. Preparation of Monobromonaphthalimide Derivative Monomer

The general structural formula of monobromonaphthalimide derivative monomer is as follows:

wherein Ar1 is the same as the Ar1 in the terminal group type single white light polymeric material.

The preparation method for monobromonaphthalimide derivative monomer is as follows:

Naphthalimide derivative Ar1H and 1-5 mole equivalents of tetra-n-butylammonium tribromide are dissolved in dichloromethane. After reacting at 0-40° C. for 10-1200 min, the reaction product is poured into water, and the organic phase is separated, washed repeatedly with water, dried, concentrated and recrystallized to obtain monobromonaphthalimide derivative monomer.

5. Preparation of Dibromoaromatic Monomer and Oligomer

The general structural formula of dibromoaromatic monomer and oligomer is as follows:

wherein Ar2 is the same as the Ar2 in the main chain type, pendant chain type and terminal group type polymeric structures.

The preparation method and reaction conditions are the same as those of 2,7-dibromofluorene and its derivative monomer.

6. Preparation of White Electroluminescent Polymeric Material

1) Preparation of main chain type white light polymeric material

The main chain type white light polymeric material is prepared using Yamamoto or Suzuki polymerizations.

Under the protection of N2gas, 1 mol of 2,7-dibromofluorene derivative monomer, 0.01-50 mol % of dibromonaphthalimide derivative monomer and 0-50 mol % of dibromoaromatic monomer are dissolved in anhydrous toluene. Then the resulted solution is dropped into a DMF solution of 1-5 mole equivalents of Ni (0). After reacting at 50-100° C. for 20-200 hr, the reaction is stopped with a mixed solution of methanol and concentrated HCl, and the reaction product is extraction-separated, concentration precipitated, extracted by solvent and vacuum-dried to produce a fibrous polymeric luminescent material.

1 mol of 9,9-disubstituted-2,7-biborate derivative monomer, 0.01-50 mol % of dibromonaphthalimide derivative monomer and 0-50 mol % of dibromoaromatic monomer were dissolved in toluene, then 2.0M solution of 5-20 mole equivalents of potassium carbonate is added. Under the protection of N2gas and at 50-100° C., 0.05-10 mol % of tetrakis(triphenylphosphine) palladium (0) is added. After reacting for 20-200 hr, the reaction is stopped with 0.1M diluted HCl solution. And the reaction product is chloroform-extracted, methanol-settled, solvent-extracted and vacuum-dried to obtain a fibrous polymeric material.

2) Preparation of Pendant Chain Type White Light Polymeric Material

The preparation methods for pendant chain type white light polymeric material using Yamamoto and Suzuki polymerizations separately are the same as those of the main chain type white tight polymeric material, except that dibromonaphthalimide derivative monomer is substituted by pendant chain type dibromonaphthalimide derivative monomer or pendant chain type 9,9-disubstituted dibromofluorene naphthalimide derivative monomer.

3) Preparation of Terminal Group Type White Light Polymeric Material

The terminal group type white light polymeric material is prepared using Yamamoto or Suzuki polymerizations.

Under the protection of N2gas, 2,7-dibromofluorene derivative monomer and 0-50 mol % of dibromoaromatic monomer Ar2 are dissolved in anhydrous toluene, then the resulting solution is dropped into a DMF solution of 1-5 mole equivalents of Ni (0). After reacting at 50-100° C. for 20-200 hr, 0.01-10 mol % of monobromonaphthalimide derivative monomer is added. After reacting at 50-100° C. for further 1-50 hr, the reaction is stopped with a mixed solution of methanol and concentrated HCl, and the reaction product is extraction-separated, concentration-precipitated, solvent-extracted and vacuum-dried to obtain a fibrous polymeric luminescent material.

1 mol of 9,9-disubstituted-2,7-biborate derivative monomer and 0-50 mol % of dibromoaromatic monomer Ar2 are dissolved in toluene, then 2.0M solution of 5-20 mole equivalents of potassium carbonate is added. Under the protection of N2gas and at 50-100° C., 0.05-10 mol % of tetrakis(triphenylphosphine) palladium (0) is added. After reaction for 1-200 hr, 0.01-10 mol % of monobromonaphthalimide derivative monomer Ar1 is added, and reacted at 50-100° C. for further 1-50 hr. The reaction is terminated with 0.1M diluted HCl solution, then the reaction product is chloroform-extracted, methanol-settled, solvent-extracted, and vacuum-dried to obtain a fibrous polymeric material.

EXAMPLES

Synthesizing of 4-bromo-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N,N-diphenyl-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-carbazolyl-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-(4,4′-dibromocarbazolyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N,N-di(4-aldophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N,N-di(4-bromostyryl)phenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N,N-(4,4′-di(4-p-tolylphenylamino)phenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N,N-(4,4′-di(4-p-tolyl-4-bromophenylamino)phenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

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

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

Synthesis of 9-phenyl-9-((4-N-(4-(4′-styryl)phenyl)-4-N-phenyl-9-(4-tributylphenyl)-1,8-naphthalimide

Synthesis of 4-N-(4-aldophenyl)-4-N-(4-(4-styryl)phenyl)-9-(4-tributylphenyl)-1,8-naphthalimide

Synthesis of 2-(2′-(4′-amino-1′,8′-naphthalimide-9′-alkyl)ethoxyl)-5-hexoxyl-1,4-dibromobenzene

Synthesis of 2-(2′-(4′-dianilino-1′,8′-naphthalimide-9′-alkyl)ethoxyl)-5-hexoxyl-1,4-dibromobenzene

Synthesis of 2-(12′-(4′-amino-1′,8′-naphthalimide-9′-alkyl)dodecoxyl-5-hexoxyl-1,4-dibromobenzene

Synthesis of 2-(12′-(4′-dianilino-1′,8′-naphthalimide-9-alkyl)dodecoxyl)-5-hexoxyl-1,4-dibromobenzene

Synthesis of 9,9-di(2-(4-amino-1,8-naphthalimide-9)-ethyl)-2,7-dibromofluorene

Synthesis of 9,9-di(2-(4-dianilino-1,8-naphthalimide-9-)ethyl)-2,7-dibromofluorene

Synthesis of 9,9-di(12-(4-amino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene

Synthesis of 9,9-di(12-(4-dianilino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene

Synthesis of 2-(6′-(4′-amino-1′,8′-naphthalimide-9′-alkyl)hexoyl)-5-hexoxyl-1,4-dibromobenzene

Synthesis of 2-(6′-(4′-dianilino-1′,8′-naphthalimide-9′-alkyl)hexoxyl)-5-hexoxyl-1,4-dibromobenzene

Synthesis of 1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-iodophenyl-1-)amino-1,8-naphthalimide-9-)-hexoxyl)benzene

Synthesis of 1,4-dibromo-2-hexoxyl-5-(6-(4-di(4′-dianilino-biphenyl-4-)amino-1,8-naphthalimide-9-)-hexoxyl)benzene

Synthesis of 1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-styrylphenyl-1-)amino-1,8-naphthalimide-9-)-hexoxyl)benzene

Synthesizing of 4-N-(4-aldophenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N-(4-(4′-bromostyryl)phenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N-(4-methylphenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesizing of 4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide

Synthesis of 4-N-(4-methylphenyl)-4-N-(4-tolyl-4′-phenylamino)phenyl-9-(4-tributylphenyl)-1,8-naphthalimide

Synthesis of 4-N-(4-methylphenyl)-4-N-(4-methyl-4′-bromophenylamino)phenyl-9-(4-tributylphenyl)-1,8-naphthalimide

Synthesis of 4-N-(4-aldophenyl)-4-N-p-bromophenyl-9-(4-tributylphenyl)-1,8-naphthalimide

Synthesis of 4-N-p-bromophenyl-4-N-(4-styryl)phenyl-9-(4-tributylphenyl)-1,8-naphthalimide

Synthesizing and Characterizing of Polymeric Electroluminescent Material P1

The assembling conditions of single-layer device (ITO/PEDOT/Polymer/Ca/Al) were as follows: the pre-cleaned ITO glass was used as anode, then a layer (40 nm) of conducting polymer, polythiophene derivative (PEDOT), was spin-coated on the anode. The ITO coated with PEDOT was vacuum dried at 110° C. for 1 hr. Then the chloroform solution containing 10 mg/ml of the polymer was spin-coated on the surface of ITO at 1500 rpm. Then, under high vacuum condition, metallic calcium (10 nm) and metallic aluminum (100 nm) were coated by vaporization. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.8V; maximum luminance, 2870 cd/m2; maximum efficiency of electroluminescence, 0.8 cd/A; color coordinate, (0.54, 0.35).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P2

The assembling conditions of single-layer device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 6.6V; maximum luminance, 10500 cd/m2; maximum efficiency of electroluminescence, 2.8 cd/A; color coordinate, (0.34, 0.48).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P3

The assembling conditions of single-layer device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.8V; maximum luminance, 18300 cd/m2; maximum efficiency of electroluminescence, 3.8 cd/A; color coordinate, (0.29, 0.45).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P4

The assembling conditions of single-layer device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.4V; maximum luminance, 12900 cd/m2; maximum efficiency of electroluminescence, 4.2 cd/A; color coordinate, (0.29, 0.45).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P5

The assembling conditions of the single-layer electroluminescent device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 4.8V; maximum luminance, 8820 cd/m2; maximum efficiency of electroluminescence, 3.9 cd/A; color coordinate for a white light, (0.30, 0.40).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P6

The assembling conditions of said single-layer electroluminescent device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.8V; maximum luminance, 9330 cd/m2; maximum efficiency of electroluminescence, 1.8 cd/A; color coordinate for a white light, (0.30, 0.46).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P7

The assembling conditions of the single-layer electroluminescent device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 4.8V; maximum luminance, 12400 cd/m2; maximum efficiency of electroluminescence, 2.7 cd/A; color coordinate for a white light, (0.29, 0.33).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P8

The assembling conditions of said single-layer electroluminescent device were the same as those of Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.4V; maximum luminance, 8880 cd/m2; maximum efficiency of electroluminescence, 1.8 cd/A; color coordinate for white light, (0.25, 0.34).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P9

The assembling conditions of the single-layer device were the same as those in Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.2V; maximum luminance, 7950 cd/m2; maximum efficiency of electroluminescence, 2.0 cd/A; color coordinate, (0.24, 0.31).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P10

The assembling conditions of the single-layer electroluminescent device were the same as those in Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.2V; maximum luminance, 7950 cd/m2; maximum efficiency of electroluminescence, 2.0 cd/A; color coordinate, (0.34, 0.39).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P11

The assembling conditions of the single-layer electroluminescent device were the same as those in Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.2V; maximum luminance, 1950 cd/m2; maximum efficiency of electroluminescence, 1.0 cd/A; color coordinate, (0.60, 0.36).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P12

The assembling conditions of the single-layer device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.0V; maximum luminance, 6550 cd/m2; maximum efficiency of electroluminescence, 2.1 cd/A; color coordinate for white light, (0.35, 0.40).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P13

The assembling conditions of the single-layer device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.8V; maximum luminance, 9050 cd/m2; maximum efficiency of electroluminescence, 2.8 cd/A; color coordinate for white light, (0.27, 0.32).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P14

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.6V; maximum luminance, 9970 cd/m2; maximum efficiency of electroluminescence, 1.7 cd/A; color coordinate, (0.26, 0.33).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P15

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.8V; maximum luminance, 13080 cd/m2; maximum efficiency of electroluminescence, 6.6 cd/A; color coordinate, (0.13, 0.50).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P16

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.2V; maximum luminance, 8450 cd/m2; maximum efficiency of electroluminescence, 1.2 cd/A; color coordinate for white light, (0.26, 0.68).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P17

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.0V; maximum luminance, 15400 cd/m2; maximum efficiency of electroluminescence, 4.2 cd/A; color coordinate for white light, (0.27, 0.34).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P18

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 4.8V; maximum luminance, 12400 cd/m2; maximum efficiency of electroluminescence, 2.2 cd/A; color coordinate for white light, (0.30, 0.34).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P19

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.2V; maximum luminance, 16880 cd/m2; maximum efficiency of electroluminescence, 2.6 cd/A; color coordinate for white light, (0.25, 0.38).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P20

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 6.8V; maximum luminance 19280 cd/m2; maximum efficiency of electroluminescence, 7.4 cd/A; color coordinate, (0.34, 0.50).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P21

The assembling conditions of the single-layer device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 6.4V; maximum luminance, 17780 cd/m2; maximum efficiency of electroluminescence, 7.2 cd/A; color coordinate, (0.34, 0.52).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P22

The assembling conditions of the single-layer device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.2V; maximum luminance, 7980 cd/m2; maximum efficiency of electroluminescence, 2.2 cd/A; color coordinate, (0.23, 0.28).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P23

The assembling conditions of the single-layer device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.4V; maximum luminance, 1770 cd/m2; maximum efficiency of electroluminescence, 0.82 cd/A; color coordinate, (0.40, 0.58).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P24

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 6.0V; maximum luminance, 4350 cd/m2; maximum efficiency of electroluminescence, 1.8 cd/A; color coordinate, (0.23, 0.21).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P25

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 6.0V; maximum luminance, 10950 cd/m2; maximum efficiency of electroluminescence, 4.3 cd/A; color coordinate, (0.28, 0.32).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P26

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.4V; maximum luminance, 2950 cd/m2; maximum efficiency of electroluminescence, 1.3 cd/A; color coordinate, (0.43, 0.56).

Synthesizing and Characterizing of Polymeric Electroluminescent Material P27

The assembling conditions of the single-layer electroluminescent device were the same as Example 37. The performances of said single-layer electroluminescent device were as follows: starting voltage, 5.0V; maximum luminance, 9940 cd/m2; maximum efficiency of electroluminescence, 3.3 cd/A; color coordinate for white light, (0.27, 0.33).