# Patent

## Title
Organic opto-electronic polymer and use thereof

## Abstract

An organic opto-electronic polymer having the structure of formula (I) is provided:




The polymer can be used in the light-emitting layer of an organic light-emitting element as a blue light-emitting material.

## Background
FIELD OF THE INVENTION
The present invention provides an organic opto-electronic material, which can be used in the light-emitting layer of an organic light-emitting element as a blue light-emitting material.
BACKGROUND OF THE INVENTION
An Organic Light Emitting Diode (OLED), first published by KODAK Co. in 1987, is a display element that utilizes the light-emitting properties of an organic light-emitting material itself to achieve the displaying effect. An OLED consists mainly of a pair of electrodes and an organic light-emitting layer, wherein the organic light-emitting layer contains a light-emitting material. When an electric current is passing between a transparent anode and a metallic cathode, an electron and a hole will combine in the light-emitting material to produce an exciton, thereby causing the light-emitting material to emit light.
Fluorenes having the following chemical structure are generally used as blue light-emitting material in an organic light-emitting diode:




(Fluorene Structure and the Numbers of Carbons on the Structure)

The main reasons for this are: (1) It has been found from previous studies that the fluorescence emitting wavelength of polyfluorenes ranges from 400 to 460 nm (blue light), and the polyfluorenes exhibit good thermal and chemical stabilities, thus making them suitable to be used as the main component of an organic blue light-emitting luminophor; and (2) In either solution state or solid state, the fluorescence quantum yield of polyfluorenes is good (60-804), and when used in light-emitting elements, the polyfluorenes will provide the light-emitting elements with a better light-emitting efficiency.

However, it was found during the development that polyfluorenes tend to stack, leading to a decrease in the light-emitting efficiency of the element. Therefore, the present invention provides a chiral fluorene polymer material to address the stacking problem associated with fluorenes.
SUMMARY OF THE INVENTION
The object of the present invention is to provide an organic opto-electronic polymer, which can be used as an organic light-emitting layer material, and has good light-emitting efficiency.
The organic opto-electronic polymer of the invention is a chiral fluorene polymer material having the structure of formula (I):




wherein:

    
    
        n1, n2 and n4 are each an integer greater than 1;
        n3 is 0 or an integer greater than 1;
        X and Y are independently a substituted or an unsubstituted C4-C60 aromatic unit or aliphatic unit; and
        G1, G2, G3 and G4 are each independently a substituted or an unsubstituted C2-C40 aromatic group or aliphatic group;
        wherein G1 and G2 are different, and when n3 is not 0, X and Y are different, and when n3 is 0, X is not
    
    









BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 represents the EL spectrum measured for an element prepared at a high temperature for a long time (120° C., 24 hours).
FIG. 2 represents the EL spectrum measured for an element prepared at a low temperature for a short time (100° C., 30 minutes).



DETAILED DESCRIPTION OF THE INVENTION
In order to enhance the light-emitting efficiency of an element, and to avoid the stacking of fluorenes, the present invention employs two different substituents, G1 and G2, for being attached at position 9 of a fluorene; and in the polymerization of the polymer, two different substituents, X and Y, are attached at positions 2 and 7 of the fluorene, respectively, so that the carbon atom at position 9 becomes a chiral center, and the is synthesized polymer may be in an R-configuration or S-configuration. When an R-configuration or S-configuration is respectively introduced into the entire polymer chain in view of the bonding order, stacking is less likely to occur because of the difference in the structure of each polymer chain.
In the polymer of formula (I) of the present invention which has at least one chiral center, n1, n2 and n4 are preferably each an integer from 1 to 300, n3 is 0 or an integer from 1 to 300; X and Y are each a substituted or an unsubstituted C6-C40 aromatic unit or aliphatic unit; and G1, G2, G3 and G4 are each a substituted or an unsubstituted C6-C30 aromatic groups or aliphatic groups, provided that G1 and G2 are different.
According to a preferred embodiment of the present invention, in the above formula (I), when n3 is not 0, X and Y are C6-C40 aromatic units, provided that they are different; and according to another preferred embodiment of the present invention, when n3 is 0, X is a C6-C40 aromatic unit, provided that X is not




According to a preferred embodiment of the present invention, X and Y are each for example, but are not limited to, the following aromatic units:







In the above formulae, each R represents a C1-C16 alkyl or C1-C16 alkoxy; and r is 0, 1, 2 or 3; and G1, G2, G3 and G4 are each a substituted or an unsubstituted C6-C30 aromatic groups, preferably phenyl or a phenyl mono-, di- or tri-substituted by C1-C16 alkyl (preferably C1-C10 alkyl) or C1-C16 alkoxy (preferably alkoxy is preferred).
The average molecular weight of the polymer of formula (I) of the present invention ranges from about 30,000 to 3,000,000, preferably from about 50,000 to 1,200,000.
The organic opto-electronic polymer of formula (I) of the present invention can be used in an organic light-emitting diode element as a light-emitting layer material. The polymer of the present invention can be incorporated into an organic light-emitting diode element as a light-emitting layer material or part of the light-emitting layer material by any method well known in the art. In other words, the material of the present invention can be blended together with other materials at various ratios prior to being coated onto an element as a light-emitting layer material. The light-emitting layer material containing the organic light-emitting material of the present invention has the property of emitting blue light, while exhibiting good light-emitting efficiency.
It is known to persons skilled in the technical field of organic light-emitting diode elements that if a light-emitting layer is doped, for example, by a doping technique, such that a fluorene polymer material having a chiral center is used as the body material of the light-emitting layer and acts as the energy-donating host, or a fluorene polymer material having a chiral center is used as a guest light-emitting dopant and acts as an energy-accepting guest, the light-emitting efficiency of the organic light-emitting diode element can be further enhanced and the light-emitting color can be adjusted.
The following examples are intended to further illustrate to the invention, but are not intended to be construed as limitations on the protection scope of the invention. All modifications and alterations which may be readily achieved by persons skilled in the art fall within the scope of the disclosure of the specification.
Preparation of Fluorene Derivatives
The 9 position of fluorene can be easily oxidized to a ketone group, thus allowing the carbon on position 9 to partially carry positive charges, then an aryl can be attached at position 9 by utilizing aryl Grignard reagent, and then a second aryl can be attached at position 9 by Friedel-Crafts reaction. In this way, a 9,9-diaryl-substituted fluorene intermediate can be prepared (such as the starting material 1, 2 or 3 as shown in Scheme I). In addition, starting material 4 can be obtained directly by the reaction of 2,7-dibromofluorene and 1-bromooctane under basic conditions (as shown in Scheme II).








Preparation of Polymeric Monomer

Starting materials 5a and 5b can be obtained by the reaction of carbazole and 1-bromo-4-t-butylbenzene under the catalysis of palladium, then bromized with N-bromosuccinimide (NBS) to afford polymeric monomers 6a and 6b (as shown in Scheme III).




Furthermore, polymeric monomer 7 can be obtained by replacing the bromine atoms of the starting material 1 with borates in the presence of n-butyl lithium (as shown in Scheme IV).




Furthermore, polymeric monomer 8 can be obtained by the reaction of the polymeric monomer 7 with 2-iodo-5-bromopyrimidine under the catalysis of palladium as shown in Scheme V).




Polymeric monomers 9a and 9b can be obtained by the reaction of 2-methyl-4-bromobenzoyl chloride with 3-methyl-4-bromobenzoyl (or 3-bromo-4-methyl benzoylhydrazine) under basic conditions, and then by the dehydration and cyclization with POCl3 (as shown in Scheme VI).




Polymerization Reactions

The starting material 2, the monomer 6a and the monomer 7 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P1 (as shown in Scheme VII). The molecular weight thereof is 42874, and the polydispersity (PDI) of the molecular weight is 1.77. Each molecular chain of this polymer on its structure has different optical active centers.




The starting material 3, the monomer 7 and the monomer 8 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P2 (as shown in Scheme VIII). The molecular weight thereof is 44068, and the polydispersity (PDT) of the molecular weight is 1.89. Each molecular chain of this polymer has different optical active centers on its structure.




The starting material 3, the monomer 6b and the monomer 7 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P3 (as shown in Scheme IX). The molecular weight thereof is 39183, and the polydispersity (PDI) of the molecular weight is 2.03. Each molecular chain of this polymer has different optical active centers on its structure.




The starting material 2, the monomer 7 and the monomer 8 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P4 (as shown in Scheme X). The molecular weight thereof is 81665, and the polydispersity (PDI) of molecular weight is 2.05. Each molecular chain of this polymer has different optical active centers on its structure.




The starting material 6b, the monomer 7 and the monomer 4 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P5 (as shown in Scheme XI). The molecular weight thereof is 83405, and the polydispersity (PDI) of molecular weight is 1.88. Each molecular chain of this polymer has different optical active centers on its structure.




The starting material 2, the monomer 9b and the monomer 7 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P6 (as shown in Scheme XII). The molecular weight thereof is 35128, and the polydispersity (PDI) of molecular weight is 1.64. Each molecular chain of this polymer has different optical active centers on its structure.




The starting material 2, the monomer 9a and the monomer 7 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P7 (as shown in Scheme XIII). The molecular weight thereof is 33401, and the polydispersity (PDI) of molecular weight is 1.58. Each molecular chain of this polymer has different optical active centers on its structure.




The starting material 2, the monomer 9a,9,10-dibromo-anthracene and the monomer 7 were mixed to achieve a Suzuki coupling reaction, providing a chiral fluorene polymer P8 (as shown in Scheme XIV). The molecular weight thereof is 197456, and the polydispersity (PDI) of the molecular weight is 2.18. Each molecular chain of this polymer has different optical is active centers on its structure.




Opto Physical Properties of Chiral Fluorenes

The synthesized polymers were dissolved in toluene at a concentration of 1% to 3% and coated onto an ITO glass surface by a spin coating method at 500 rpm to 3000 rpm to form a thin film. The film was then plated with an aluminum electrode under a pressure of 5.0×10−6 torr, driven by applying 3 to 20 volts, and measured for the electroluminescent spectrum with a PR650 photometer from KODAK. FIG. 1 and FIG. 2 represent the EL spectra for the elements prepared at a high temperature for a long time (120° C., 24 hours) and at a low temperature for a short time (100° C., 30 minutes), respectively.







TABLE







Physical Properties of Polymers
















Maximum
Maximum






Absorption
Emission


Polymer
Mw
Mn
Mw/Mn
Wavelength
Wavelength















P1
42874
24130
1.77
389
421


P2
44068
23346
1.89
388
421


P3
89183
39833
2.03
386
420


P4
81665
39833
2.05
390
421


P5
83405
44280
1.88
387
419


P6
35128
21468
1.64
386
424


P7
33401
21117
1.58
385
424


P8
197456
90466
2.18
389
446





Note:


Absorption and emission wavelength data were measured for the polymers dissolved in chloroform.






It can be found from the data of FIG. 1 and FIG. 2 that, the element prepared from the polymeric thin film by heating at a high temperature for a long time (120° C., 24 hours) is not significantly different from that prepared by heating at a low temperature for a short time (100° C., 30 minutes). Therefore, it can be concluded that the chiral centers introduced according to the present invention prevent the stacking of the polymeric chains.

## Claims

1. An organic opto-electronic polymer having a structure of formula (I):




wherein:
n1, n2 and n4 are each an integer greater than or equal to 1;
n3 is 0 or an integer greater than 1;
X and Y are independently a substituted or an unsubstituted C4-C60 aromatic units; and
wherein G1, G2, G3 and G4 are each phenyl or a phenyl mono-, di- or tri-substituted by C1-C16 alkyl or C1-C16 alkoxy;
wherein G1 and G2 are different, and when n3 is not 0, X and Y are different, and when n3 is 0, X is not

2. The organic opto-electronic polymer according to claim 1, having at least one chiral center.

3. The organic opto-electronic polymer according to claim 1, wherein n1, n2 and n4 are each an integer from 1 to 300; and n3 is 0.

4. The organic opto-electronic polymer according to claim 1, wherein n3 is 0; X is a C6-C40 aromatic unit, but is not

5. The organic opto-electronic polymer according to claim 1, having an average molecular weight ranging from 30,000 to 3,000,000.

6. The organic opto-electronic polymer according to claim 5, having an average molecular weight ranging from 40,000 to 1,200,000.

7. A light-emitting layer for use in an organic light-emitting element, comprising the organic opto-electronic polymer according to claim 1.

8. An organic opto-electronic polymer having a structure of formula (I):




wherein:
n1, n2 and n4 are each an integer greater than or equal to 1;
n3 is 0;
X is C4-C60 aromatic unit, but is not




and

G1, G2, G3 and G4 are each phenyl or a phenyl mono-, di- or tri-substituted by C1-C16 alkyl or C1-C16 alkoxy, and G1 and G2 are different.

9. The organic opto-electronic polymer according to claim 8, having at least one chiral center.

10. The organic opto-electronic polymer according to claim 8, wherein n1, n2 and n4 are each an integer from 1 to 300.

11. The organic opto-electronic polymer according to claim 8, wherein X is a C6-C40 aromatic unit, but is not

12. The organic opto-electronic polymer according to claim 8 having an average molecular weight ranging from 30,000 to 3,000,000.

13. The organic opto-electronic polymer according to claim 8 having an average molecular weight ranging from 40,000 to 1,200,000.

14. A light-emitting layer for use in an organic light-emitting element comprising the organic opto-electronic polymer according to claim 8.