CN1910261A - Organic electroluminescent polymer having 9,9-di(fluorenyl)-2,7-fluorenyl unit and organic electroluminescent device manufactured using the same - Google Patents

Abstract

An organic electroluminescent polymer having a 9,9-bis(fluorenyl)-2,7-fluorenyl unit and an organic electroluminescent device using the polymer are disclosed herein. More specifically, the present invention provides a 9,9-bis(fluorenyl)-2,7 -Organic electroluminescent polymer of fluorenyl unit and organic electroluminescent device using the organic electroluminescent polymer. The electroluminescence polymer is suitable as a host material for high-purity blue light, green light and red light, and has high solubility, high thermal stability and high quantum efficiency.

Description

Organic electroluminescent polymer having 9,9-bis(fluorenyl)-2,7-fluorenyl unit and organic electroluminescent device prepared using the polymer

technical field

The invention relates to an organic electroluminescent polymer with 9,9-bis(fluorenyl)-2,7-fluorenyl unit and an organic electroluminescent device prepared by using the polymer. More specifically, the present invention relates to a 9,9-bis(fluorenyl)-2,7- An organic electroluminescent polymer of fluorenyl units and an organic electroluminescent device prepared by using the organic electroluminescent polymer.

Background technique

With recent great advances in the fields of optical communication and multimedia, progress toward a highly information-intensive society is accelerating. Therefore, optoelectronic devices utilizing photon-to-electron conversion or electron-to-photon conversion have been valued in the modern information electronics industry.

Semiconductor optoelectronic devices are classified into electroluminescent devices, light receiving devices, and combinations thereof.

Most of the newly manufactured displays are light-receiving types, however, electroluminescent displays have self-luminous properties, so they do not require a backlight to exhibit fast response and high brightness. Therefore, electroluminescent displays are considered to be next-generation displays.

Electroluminescent devices are classified into inorganic light emitting devices and organic light emitting devices according to the type of light emitting layer material.

Organic electroluminescence (EL) means that energy generated when electrons and holes respectively migrated from a cathode and an anode are combined in an organic material by an electric field applied to the organic material is emitted in the form of light. Such electroluminescence of organic materials was reported by Pope et al. in 1963. Since Tang et al. of Eastmann Kodak used a colorant with an alumina-quinone p-conjugated structure in 1987 to produce a quantum efficiency of 1% at or below 10 volts and a brightness of 1000 candela/square meter (cd/ m ² ) of multilayer light-emitting devices, a lot of research is going on. Such a device is advantageous because various materials can be easily synthesized and toned according to a simple synthetic route. However, processability or stability is low, and molecular rearrangement is caused by Joule heat generated by the light-emitting layer when a voltage is applied to adversely affect the light-emitting efficiency or service life of the device. Organic electroluminescent devices having a polymer structure capable of alleviating the above-mentioned problems have therefore been proposed.

Based on this, FIG. 1 shows a conventional organic electroluminescent device including substrate/anode/hole transport layer/light emitting layer/electron transport layer/cathode.

As shown in FIG. 1 , an anode 12 is formed on a substrate 11 . On the anode 12, a hole transport layer 13, a light emitting layer 14, an electron transport layer 15, and a cathode 16 are sequentially formed. Likewise, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 are organic thin films made of organic compounds. The organic electroluminescent device having the above structure operates as follows:

When a voltage is applied to the anode 12 and the cathode 16 , holes injected from the anode 12 move to the light emitting layer 14 through the hole transport layer 13 . At the same time, electrons are injected from the cathode 16 into the light-emitting layer 14 through the electron-transporting layer 15 , and carriers (carriers) recombine in the region of the light-emitting layer 14 to generate excitons. The excitons change from the excited state to the ground state, and the fluorescent molecules in the light-emitting layer emit light, thereby forming an image.

The organic material used to form the organic film of the EL device may be a low-molecular-weight or high-molecular-weight organic material.

When a low-molecular-weight organic material is used, it is easy to purify the material to an impurity-free state, so the luminescent performance is good. However, low-molecular-weight materials do not allow inkjet printing or spin coating, and have poor heat resistance, thus being damaged or recrystallized by heat generated during device operation.

On the other hand, when a polymer material (that is, a polymer) is used, the energy levels are divided into a conduction band and a valence band, and the wave functions of p electrons present in the backbone (backbone) overlap each other. The band gap between the conduction band and the valence band determines the semiconducting properties of the polymer, so controlling the band gap can realize full-color display. Such polymers are called p-conjugated polymers.

The EL based on the conjugated polymer poly(p-phenylenevinylene) (poly(p-phenylenevinylene), hereinafter referred to as "PPV") was carried out in 1990 by a research group led by Professor R.H.Friend (Cambridge University, England). The first development of the device has stimulated intensive and active research on organic polymers with semiconducting properties. In addition to being superior to low molecular weight materials in heat resistance, polymeric materials are used in large surface displays due to their ability to be inkjet printed or spin coated. It has been reported that PPV and polythiophene (Pth) derivatives introduced with various functional moieties have high processability and exhibit various colors. However, although these PPV and Pth derivatives can be efficiently applied to emit red and green light, it is difficult to efficiently emit blue light. It has been reported that polyphenylene derivatives and polyfluorene derivatives are blue light emitting materials. Polyphenylene has high oxidation stability and high thermal stability, but has poor luminous efficiency and solubility.

Regarding polyfluorene derivatives, related prior art is as follows:

US 6255449 discloses a 9-substituent-2,7-dihalofluorene (9-substituted-2,7-dihalofluorene) compound suitable for use as a light-emitting material such as a light-emitting layer or a carrier transport layer in a light-emitting diode and its oligomers and polymers.

US 6309763 and US 6605373 disclose electroluminescent copolymers containing fluorine groups and amine groups in the repeating units. According to US 6309763, such copolymers can be used in the light-emitting layer or the hole-transporting layer in electroluminescent devices.

WO 02/77060 discloses conjugated polymers containing spirobifluorene units. According to this document, the polymers disclosed therein show an improved property profile as electroluminescent material in electronic components such as Polymer Light-emitting Diodes (PLEDs).

Contents of the invention

As mentioned above, although the research on the use of polyfluorene derivatives as blue light-emitting polymers is being comprehensively carried out, the minimization of the interaction of excitons generated between adjacent molecules and the improvement of efficiency and lifetime are still to be realized. task.

In order to avoid the problems encountered in the prior art, the inventors of the present invention have carried out thorough and thorough research on organic electroluminescent polymers, and found that electroluminescent polymers contain disubstituted fluorenyl groups at their 9 positions. Fluorene units, so that the electroluminescent polymer can be used as a novel host material for blue, green and red light emission, while minimizing the interaction between molecules and solving the shortcomings of conventional polyfluorenes (PFs), it has Excellent thermal stability, high luminous efficiency, and high solubility, and an electroluminescent device using the electroluminescent polymer can be produced, thereby completing the present invention.

Therefore, an object of the present invention is to provide an organic electroluminescent polymer as a host material required to realize blue, green and red light emission, which exhibits It has the advantages of high thermal and oxidation stability, low molecular interaction, easy energy transfer, and high luminous efficiency.

Another object of the present invention is to provide an organic electroluminescent device using the organic electroluminescent polymer.

In order to achieve the above object, the present invention provides an organic electroluminescent polymer with 9,9-bis(fluorenyl)-2,7-fluorenyl unit, the organic electroluminescent polymer is shown in formula 1 below:

Formula 1

Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each is a linear or branched chain alkyl group of 1-20 carbon atoms; Or an aryl group substituted by at least one substituent in the group consisting of branched alkyl and alkoxy; having at least one heterogeneous group selected from the group consisting of F, S, N, O, P and Si A straight-chain or branched chain alkyl or alkoxy group of 1 to 20 carbon atoms; consisting of straight or branched chain alkyl and alkoxy groups of 1 to 20 carbon atoms containing at least one heteroatom An aryl group substituted by at least one substituent in the group, the heteroatom is selected from the group consisting of F, S, N, O, P and Si; the heterocyclic part having 2-24 carbon atoms, An aryl group that is unsubstituted or substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups of 1 to 20 carbon atoms; a heterocyclic moiety having 2 to 24 carbon atoms An aryl group substituted by at least one substituent selected from the group consisting of linear or branched chain alkyl and alkoxy groups of 1-20 carbon atoms containing at least one heteroatom selected from In the group consisting of F, S, N, O, P and Si; substituted or unsubstituted 3-40 carbon atoms trialkylsilyl group (trialkylsilylgroup) substituted or unsubstituted 3-40 carbon atoms Arylsilyl; substituted or unsubstituted carbazolyl of 12-60 carbon atoms; substituted or unsubstituted phenothiazinyl of 6-60 carbon atoms; or substituted or unsubstituted 6-60 carbon Atomic arylamino group;

R ₅ , R ₆ , R ₇ and R ₈ are the same or different, and each is a straight-chain or branched chain alkyl or alkoxy group with 1-20 carbon atoms in hydrogen; unsubstituted or selected from 1-20 carbon atoms An aryl group substituted by at least one substituent in the group consisting of linear or branched alkyl and alkoxy; having at least one substituent selected from the group consisting of F, S, N, O, P and Si A straight-chain or branched chain alkyl or alkoxy group of 1-20 carbon atoms containing at least one heteroatom; An aryl group substituted by at least one substituent in the group consisting of radicals, the heteroatoms being selected from the group consisting of F, S, N, O, P and Si; a heterocyclic ring having 2-24 carbon atoms Partial, unsubstituted or aryl group substituted by at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups of 1-20 carbon atoms; aryl groups having 2-24 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of straight-chain or branched-chain alkyl and alkoxy groups of 1 to 20 carbon atoms containing at least one heteroatom in the heterocyclic portion, said hetero Atoms selected from the group consisting of F, S, N, O, P and Si; substituted or unsubstituted trialkylsilyl groups of 3-40 carbon atoms; substituted or unsubstituted 3-40 carbon atoms arylsilyl; substituted or unsubstituted carbazolyl of 12-60 carbon atoms; substituted or unsubstituted phenothiazinyl of 6-60 carbon atoms; or substituted or unsubstituted 6-60 Aromatic amino groups of carbon atoms;

a, b, c and d are the same or different, each being an integer from 1 to 3;

Ar is selected from the group consisting of substituted or unsubstituted aromatic moieties of 6-60 carbon atoms, substituted or unsubstituted heteroaromatic moieties of 2-60 carbon atoms, and combinations thereof;

l is an integer of 1 to 100,000, m is an integer of 0 to 100,000, and n is an integer of 1 to 100,000.

The present invention also provides an organic electroluminescent device, which has at least one layer containing the above-mentioned polymer between the anode and the cathode, wherein the layer is a hole transport layer, a light-emitting layer, an electron transport layer layer or hole blocking layer.

The invention provides an organic electroluminescent polymer with 9,9-bis(fluorenyl)-2,7-fluorenyl unit and an organic electroluminescent device prepared by using the polymer. The electroluminescent polymer of the present invention has high thermal stability, high luminous efficiency and high solubility, and can minimize the interaction of molecules. In addition, the above-mentioned polymers can reduce the disadvantages of conventional polyfluorene-based polymers, and can be used as host materials for blue, green and red luminescence of electroluminescence devices, thus exhibiting better luminescence characteristics.

Description of drawings

The above and other objects, features and other advantages of the present invention will be more clearly understood through the following detailed description in conjunction with the accompanying drawings.

Fig. 1 is a schematic cross-sectional view showing the structure of a conventional organic electroluminescent device comprising substrate/anode/hole transport layer/emissive layer/electron transport layer/cathode;

Fig. 2 is a schematic diagram showing the monomer synthesis reaction of the electroluminescent polymer represented by formula 2 according to the present invention;

Fig. 3 is a schematic diagram showing the monomer synthesis reaction of the electroluminescent polymer represented by formula 4 according to the present invention;

Fig. 4 is the ¹ H-NMR spectrum of the monomer represented by compound (2) according to the present invention;

Fig. 5 is according to the ¹ H-NMR spectrum of the electroluminescence polymer represented by formula 2 according to the present invention;

Fig. 6 is according to the photoluminescence (photoluminescence, PL) spectrum of electroluminescence polymer represented by formula 2 in chloroform solution and film respectively according to the present invention;

Fig. 7 is the electroluminescence (electroluminescence, EL) spectrum of the electroluminescence device prepared by the electroluminescence polymer shown in formula 2 according to the present invention;

Fig. 8 is according to the photoluminescence (PL) spectrum of electroluminescent polymer represented by formula 4 in chloroform solution and film respectively according to the present invention;

9 is an electroluminescent (EL) spectrum of an electroluminescent device prepared using the electroluminescent polymer represented by Formula 4 according to the present invention.

Detailed ways

The present invention will be described in detail below with reference to the accompanying drawings.

The invention provides an organic electroluminescent polymer with 9,9-bis(fluorenyl)-2,7-fluorenyl units and an organic electroluminescent device prepared by using the polymer. The electroluminescent polymer can be It is used as a high-purity blue, green and red luminescent host material, and has high solubility, high thermal stability and high quantum efficiency.

The organic electroluminescent polymer provided by the present invention is a material with high thermal stability, high light stability, high solubility, high quantum efficiency and excellent film-forming property, and is characterized in that, as the main body substituent (bulky substituent) The fluorenyl group is introduced at the 9-position of fluorene as the main chain, so the substituent has the same structure as the main chain. Therefore, the arrangement between the main chain and the substituents becomes random, and the formation of intermolecular excited atoms by the substituents is also suppressed, thereby avoiding aggregation and/or excitation, which is the biggest problem encountered in polyfluorene-based polymers. Formation of state atoms. Moreover, intramolecular or intermolecular energy can be transferred from substituents with short wavelengths to the main chain.

In addition, the 9-position of fluorene used as the main chain utilizes the host fluorenyl substituent to play a role in controlling the rotation or electronic vibration mode to thoroughly reduce the non-radiative attenuation. Accordingly, the organic electroluminescent polymers of the present invention exhibit high color purity, high luminescence and high efficiency.

According to the present invention, the organic electroluminescent polymer has 9,9-bis(fluorenyl)-2,7-fluorenyl units, as shown in the following formula 1:

Formula 1

Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each is a linear or branched chain alkyl group of 1-20 carbon atoms; Or an aryl group substituted by at least one substituent in the group consisting of branched alkyl and alkoxy; having at least one heterogeneous group selected from the group consisting of F, S, N, O, P and Si A straight-chain or branched chain alkyl or alkoxy group of 1 to 20 carbon atoms; consisting of straight or branched chain alkyl and alkoxy groups of 1 to 20 carbon atoms containing at least one heteroatom An aryl group substituted by at least one substituent in the group, the heteroatom is selected from the group consisting of F, S, N, O, P and Si; the heterocyclic part having 2-24 carbon atoms, An aryl group that is unsubstituted or substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups of 1 to 20 carbon atoms; a heterocyclic moiety having 2 to 24 carbon atoms An aryl group substituted by at least one substituent selected from the group consisting of linear or branched chain alkyl and alkoxy groups of 1-20 carbon atoms containing at least one heteroatom selected from In the group consisting of F, S, N, O, P and Si; substituted or unsubstituted trialkylsilyl groups of 3-40 carbon atoms; substituted or unsubstituted aryl groups of 3-40 carbon atoms A silyl group; a substituted or unsubstituted carbazolyl group of 12-60 carbon atoms; a substituted or unsubstituted phenothiazinyl group of 6-60 carbon atoms; or a substituted or unsubstituted 6-60 carbon atom Aromatic amino group;

R ₅ , R ₆ , R ₇ and R ₈ are the same or different, and each is a straight-chain or branched chain alkyl or alkoxy group with 1-20 carbon atoms in hydrogen; unsubstituted or selected from 1-20 carbon atoms An aryl group substituted by at least one substituent in the group consisting of linear or branched alkyl and alkoxy; having at least one substituent selected from the group consisting of F, S, N, O, P and Si A straight-chain or branched chain alkyl or alkoxy group of 1-20 carbon atoms containing at least one heteroatom; An aryl group substituted by at least one substituent in the group consisting of radicals, the heteroatoms being selected from the group consisting of F, S, N, O, P and Si; a heterocyclic ring having 2-24 carbon atoms Partial, unsubstituted or aryl group substituted by at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups of 1-20 carbon atoms; aryl groups having 2-24 carbon atoms An aryl group substituted with at least one substituent selected from the group consisting of straight-chain or branched-chain alkyl and alkoxy groups of 1 to 20 carbon atoms containing at least one heteroatom in the heterocyclic portion, said hetero Atoms selected from the group consisting of F, S, N, O, P and Si; substituted or unsubstituted trialkylsilyl groups of 3-40 carbon atoms; substituted or unsubstituted 3-40 carbon atoms arylsilyl; substituted or unsubstituted carbazolyl of 12-60 carbon atoms; substituted or unsubstituted phenothiazinyl of 6-60 carbon atoms; or substituted or unsubstituted 6-60 Aromatic amino groups of carbon atoms;

a, b, c and d are the same or different, each being an integer from 1 to 3;

Ar is selected from the group consisting of substituted or unsubstituted aromatic moieties of 6-60 carbon atoms, substituted or unsubstituted heteroaromatic moieties of 2-60 carbon atoms, and combinations thereof;

l is an integer of 1 to 100,000, m is an integer of 0 to 100,000, and n is an integer of 1 to 100,000. Preferably, the ratio of l to m is from 5:95 to 95:5.

According to the present invention, preferably said R ₁ , R ₂ , R ₃ and R ₄ are respectively selected from the following groups:

In addition, preferably said _R5 and _R6 are respectively selected from the following groups:

in,

(i) The R ₉ and R ₁₀ are the same or different, and are respectively straight-chain or branched-chain alkyl groups with 1-20 carbon atoms.

The above-mentioned fluorenyl groups are representatively selected from the following groups:

(ii) R is _hydrogen , or a linear or branched alkyl, alkoxy or trialkylsilyl group of 1-20 carbon atoms;

R ₁₂ and R ₁₃ are the same or different, and are respectively linear or branched chain alkyl groups of 1-20 carbon atoms;

X is O or S;

Y and Z are N; and

a is an integer of 1 to 3;

The above-mentioned aryl group having a heterocyclic moiety is typically selected from the following groups:

(iii) R ₁₄ , R ₁₅ and R ₁₆ are the same or different, and are respectively linear or branched chain alkyl or alkoxy groups of 1-20 carbon atoms, or unsubstituted or selected from 1-20 carbon atoms An aryl group substituted by at least one substituent from the group consisting of straight-chain or branched-chain alkyl and alkoxy;

R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are the same or different, and are hydrogen, straight-chain or branched-chain alkyl or alkoxy of 1-20 carbon atoms, or unsubstituted or composed of An aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy.

The above-mentioned silyl groups, carbazoles, phenothiazines and arylamines can be representatively selected from the following groups:

In addition, it is preferred that said _R7 and _R8 are respectively selected from the following groups:

According to the present invention, it is preferred that Ar is selected from the following groups: (i) substituted or unsubstituted arylene groups of 6-60 carbon atoms; (ii) substituted or unsubstituted heterogeneous groups of 2-60 carbon atoms Cycloarylene, wherein the aromatic ring contains at least one heteroatom selected from the group consisting of N, S, O, P and Si; (iii) substituted or unsubstituted arylene of 6-60 carbon atoms (arylenevinylene); (iv) substituted or unsubstituted arylamine of 6-60 carbon atoms; (v) substituted or unsubstituted carbazolyl of 12-60 carbon atoms; and (vi) their combination,

wherein Ar may include a substituent such as a straight chain or branched chain alkyl or alkoxy group of 1-20 carbon atoms; An aryl group substituted by at least one substituent in the group consisting of an alkyl group and an alkoxy group; a cyano group (-CN) or a silyl group.

More specifically,

(i) In a substituted or unsubstituted arylene group of 6-60 carbon atoms, when Ar is phenylene or fluorenylene, Ar can typically be selected from the following groups:

(ii) When Ar is a substituted or unsubstituted heterocyclic arylene group of 2-60 carbon atoms, Ar can typically be selected from the following groups:

(iii) When Ar is a substituted or unsubstituted arylene vinylene group of 6-60 carbon atoms, Ar can be representatively selected from the following groups:

(iv) When Ar is a substituted or unsubstituted arylamino group with 6-60 carbon atoms, Ar can typically be selected from the following groups:

Wherein R ₂₃ , R ₂₄ and R ₂₅ are the same or different, and are hydrogen, linear or branched chain alkyl or alkoxy groups of 1-20 carbon atoms, or unsubstituted or selected from 1-20 carbon atoms An aryl group substituted with at least one substituent from the group consisting of straight-chain or branched-chain alkyl and alkoxy. More preferably, Ar is selected from the following group:

(v) When Ar is a substituted or unsubstituted carbazolyl group with 12-60 carbon atoms, Ar can typically be selected from the following groups:

Wherein R _is a straight chain or branched chain alkyl or alkoxy group of 1-20 carbon atoms, or is unsubstituted or is selected from a straight chain or branched chain alkyl group and alkoxy group of 1-20 carbon atoms An aryl group substituted by at least one substituent in the group consisting of.

In addition, when the Ar is (iv) a substituted or unsubstituted aromatic amino group of 6-60 carbon atoms, the content of Ar in the electroluminescent polymer is preferably about 5-15 mol%.

The preparation of the organic electroluminescent polymer of the present invention includes, for example, preparation of monomers by alkylation, bromination, Grignard reaction, Wittig reaction, etc., followed by carbon-carbon coupling reactions such as Yamamoto coupling reaction or Suzuki coupling reaction to prepare organic electroluminescent polymers. The number average molecular weight of the obtained polymer is 1500-10000000, and the molecular weight distribution is 1-50.

The organic electroluminescent polymer of the present invention can be used as blue, green and red light-emitting hosts, has excellent thermal stability, oxidation stability and solubility, and exhibits low molecular interaction due to suppression of electronic vibrational modes, The advantages of easy energy transfer and high luminous efficiency.

According to the present invention, the organic electroluminescent polymer can be used as a forming material of a light emitting layer, a hole transport layer, an electron transport layer or a hole blocking layer located between a pair of electrodes of an electroluminescent device.

The organic electroluminescent device includes a basic structure: anode/luminescent layer/cathode, and optionally a hole transport layer and an electron transport layer.

Referring to Fig. 1, Fig. 1 is a schematic cross-sectional view showing a typical structure of an organic electroluminescent device comprising a substrate/anode/hole transport layer/luminescent layer/electron transport layer/cathode, for example using the organic electroluminescent polymer of the present invention The organic electroluminescent device was prepared as follows.

The electrode material of the anode 12 is coated on the substrate 11 .

As the substrate 11, any substrate used for conventional organic electroluminescent devices can be used. A glass substrate or a transparent plastic substrate having excellent transparency, surface flatness, easy handling, and water resistance is preferably used.

In addition, the electrode material of the anode 12 includes transparent and highly conductive indium tin oxide (ITO), tin oxide (SnO ₂ ), and zinc oxide (ZnO).

The hole transport layer 13 may subsequently be formed on the anode 12 by vacuum deposition or sputtering, and then the light emitting layer 14 may be formed by a solution coating method such as spin coating or inkjet printing. An electron transport layer 15 is also formed on the light emitting layer 14, and then a cathode 16 is formed. Accordingly, the thickness of the light-emitting layer 14 is from about 5 nanometers to about 1 millimeter, preferably from about 10 to about 500 nanometers. The hole transport layer and the electron transport layer are about 10-10000 Angstroms (A) thick.

The electron transport layer 15 is obtained by using a general electron transport layer forming material or by vacuum-depositing, sputtering, spin coating, or inkjet printing the compound represented by Formula 1.

The hole transport layer 13 and the electron transport layer 15 function to efficiently transfer carriers to the light-emitting polymer to improve the light-emitting efficiency of the light-emitting polymer. In addition, there are no particular limitations on the forming materials of the hole transport layer 13 and the electron transport layer 15 . For example, hole-transporting layer materials include PEDOT:PSS as a layer of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with (poly(styrenesulfonic acid) (PSS), and N,N' -bis(3-methylphenyl)-N,N-diphenyl-[1,1'-biphenyl]-4,4'-diamine (TPD), and electron transport layer materials include trihydroxyquinone Aluminum trihydroxyquinoline (Alq3), 1,3,4-oxadiazole derivative PBD (2-(4-biphenyl)-5-phenyl-1,3,4-oxadiazole), quinoxa Phenyl derivatives TPQ (1,3,4-tris[(3-phenyl-6-trifluoromethyl)quinoxalin-2-yl]benzene) and triazole derivatives.

When the organic electroluminescent polymer is solution-coated to form the layer, the organic electroluminescent polymer can be combined with a polymer having a conjugated double bond such as polyphenylene vinylene and polyparaphenylene. ) and other fluorenyl polymers. A binder resin can be mixed and used as needed. Examples of the binder resin include polyvinylcarbazole, polycarbonate, polyester, polyarylate, polystyrene, acryl polymer, methalidene polymer, methacryl polymer, polybutyral, polyvinyl acetal, diallyl phthalate polymer, phenol resin, epoxy resin, silicone resin, polysulfone resin or urea resin. The resins may be used alone or in combination.

It is also possible to selectively form a hole blocking layer made of lithium fluoride (LiF) by, for example, vacuum deposition, so as to control the transfer rate of holes in the light-emitting layer 14 and improve the combination efficiency between electrons and holes. effect.

Finally, the electrode material of the cathode 16 is coated on the electron transport layer 15 .

Metals used to form low work function cathodes include, for example, lithium (Li), magnesium (Mg), calcium (Ca), aluminum (Al), and Al:Li.

The organic electroluminescence device of the present invention is fabricated in the order of anode/hole transport layer/light emitting layer/electron transport layer/cathode, or vice versa, namely cathode/electron transport layer/light emitting layer/hole transport layer/anode.

In addition, the organic electroluminescent polymer of the present invention can be used not only as a high molecular weight organic electroluminescent device material, but also as a light conversion material for a photodiode or a semiconductor material for a polymer thin film transistor (ThinFilm Transistor, TFT).

According to the present invention, the organic electroluminescent polymer site has a fluorenyl group introduced as a bulky substituent at the 9-position of fluorene as a main chain. The substituent thus has the same structure as the main chain, so a random arrangement between the main chain and the substituent occurs. It is also possible to suppress the formation of intermolecular excimer atoms by substituents, thereby avoiding aggregation or formation of excimer atoms, which is the biggest problem in the field of polyfluorenyl groups. Moreover, intramolecular or intermolecular energy can be transferred from substituents with short wavelengths to the main chain. By introducing a substituted fluorenyl group at the 9-position of the fluorenyl group as the main chain, the rotation or electronic vibration mode is controlled, thereby significantly reducing non-radiative attenuation to exhibit high thermal stability, photostability, solubility, film-forming property, and quantum efficiency . Therefore, the organic electroluminescent polymer of the present invention and the organic electroluminescent device prepared using the polymer can exhibit high color purity, high luminescence and high efficiency.

The present invention can be better understood by the following examples, which are provided for the purpose of illustration and should not be construed as limiting the present invention.

The following Examples 1-4 were carried out according to the reactions shown in FIG. 2 .

Example 1 Synthesis of 9-(9,9-dihexylfluoren-2-yl)-2,7-dibromofluoren-9-alcohol (1)

5.64 g of magnesium was put into a 1000 ml three-neck flask, and 80 g of 9,9-dihexyl-2-bromofluorene dissolved in 300 ml of tetrahydrofuran (THF) was slowly added dropwise to prepare the Grignard reagent. When the temperature of the reaction chamber dropped to -40°C or lower, 52 g of 2,7-dibromofluorenone was added to the reaction bath under a nitrogen atmosphere. The temperature was slowly raised to room temperature, followed by stirring for 10 hours. The resulting reaction solution was poured into water, followed by extraction using diethyl ether. The solvent was evaporated off using a rotary evaporator. Column chromatography gave 60 g (58%) of 9-(9,9-dihexylfluoren-2-yl)-2,7-dibromofluoren-9-ol (1).

Example 2 Synthesis of 9,9-bis(9,9-dihexylfluoren-2-yl)-2,7-dibromofluorene (2)

In a 2-liter round bottom flask, 50 g of compound (1) and 200 g of 9,9-dihexylfluorene were dissolved in 1000 ml of dichloromethane, and then cooled to 0°C. A solution of 10 ml of methanesulfonic acid dissolved in 100 ml of dichloromethane was slowly added to the reaction solution with stirring, and stirring was continued for 2 hours. The resulting reaction solution was poured into water, followed by extraction using diethyl ether. The solvent was evaporated off using a rotary evaporator. Column chromatography was performed to obtain 60 g (58%) of 9,9-bis(9,9-dihexylfluoren-2-yl)-2,7-dibromofluorene (2).

Embodiment 3 9, the synthesis of 9-bis(9,9-dihexylfluoren-2-yl) fluorene-2,7-diboronic acid (3)

In a 250 ml round bottom flask, 10 g of compound (2) was dissolved in 60 ml of tetrahydrofuran, and then cooled to -70°C. 2 equivalents of 2.5 mol/L n-butyllithium were slowly added to the above reaction solution, and reacted at low temperature (-70°C to -40°C) for 2 hours. 4 equivalents of triethyl borate were also added at the same temperature, and the obtained reaction solution was left to stand for 12 hours. The resulting reaction solution was added to a 3 mol/L aqueous hydrochloric acid solution, followed by stirring for 4 hours and extraction with diethyl ether. The solvent was removed using a rotary evaporator to give a solidified mass which was washed several times with toluene to yield 3.6 g (39%) of 9,9-bis(9,9-dihexylfluoren-2-yl)fluorene-2, 7-Diboronic acid (3).

Example 4 Synthesis of 9,9-bis(9,9-dihexylfluoren-2-yl)fluorene-2,7-diboronic acid ethylene glycol ester (4)

2 g of compound (3), 3 equivalents of ethylene glycol, and 50 mL of anhydrous toluene were added to a 100 mL round bottom flask equipped with a Dean-Stark apparatus. Then, reflux was performed for 24 hours to remove water. The resulting substance was recrystallized from toluene to obtain 1.8 g of ethylene glycol 9,9-bis(9,9-dihexylfluoren-2-yl)fluorene-2,7-diboronate (4).

The following examples 5-8 were carried out according to the reaction scheme shown in FIG. 3 .

Embodiment 5 2-bromo-9, the synthesis of 9-two (4-hydroxyphenyl) fluorene (5)

10 g of 2-bromofluorene, 2 equivalents of methanesulfonic acid and 100 g of phenol were put into a 500 ml round bottom flask, and then stirred at 150°C for 24 hours. The reaction solution was cooled and mixed with water to filter solids. The solid was then recrystallized from toluene to give 12 g of 2-bromo-9,9-bis(4-hydroxyphenyl)fluorene (5).

Embodiment 6 2-bromo-9, the synthesis of 9-two (4-(2-methyl) butyl oxygen) phenyl) fluorene (6)

In a 250 ml round bottom flask, 10 g of compound (5) and 2.2 equivalents of 2-methylbutyl p-toluenesulfonate were dissolved in 100 ml of dimethyl sulfoxide (Dimethyl Sulphoxide, DMSO) to obtain the reaction solution, to which 2.3 equivalents of potassium tert-butoxide (t-BuOK) was slowly added. After reacting at 70° C. for 12 hours, the resulting reaction solution was poured into 500 ml of water, followed by extraction with dichloromethane, and the solvent was removed using a rotary evaporator. Column chromatography was performed using a mixed solvent of hexane and ethyl acetate to obtain 14 g of 2-bromo-9,9-bis(4-(2-methyl)butyloxy)phenyl)fluorene (6).

Example 7 4,4-dibromobiphenyl-2-yl-two [9,9-bis(4-(2-methyl)butyloxy)phenyl)fluoren-2-yl-methanol (7) synthesis

In a 250-ml three-necked flask, 18 grams of compound (6) were dissolved in 300 milliliters of tetrahydrofuran, then the reactor was cooled to -40°C, and 2.5 mol/liter of n-butyllithium was slowly added dropwise thereto, then stirred for 2 Hour. The temperature of reaction bath is down to-40 ℃ or lower, under nitrogen atmosphere, 0.4 equivalent methyl-(2-bromo-4-bromophenyl) benzoate is joined in reaction bath, be warming up to room temperature gradually, then Stir for 10 hours. The reaction solution was poured into water, followed by extraction with diethyl ether. Solvent was removed using a rotary evaporator. Separated by column chromatography, 17 grams of 4,4-dibromobiphenyl-2-yl-bis[9,9-bis(4-(2-methyl)butyloxy)phenyl]fluoren-2-yl- Methanol (7).

Example 8 2,7-dibromo-[9,9-bis[9,9-bis(4-(2-methyl)butyloxyphenyl)fluoren-2-yl-]fluorene](8) synthesis

10 g of compound (7) and 100 ml of acetic acid were added to a 250 ml round bottom flask, 5 drops of 35% by weight hydrochloric acid were added thereto, and then refluxed for 12 hours. The reaction solution was cooled to room temperature to filter the solid. The filtered solid was then washed with a mixture of water and methanol, and recrystallized in a mixed solution of methylene chloride and ethanol to give 2,7-dibromo-[9,9-bis[9,9-bis(4-( 2-methyl)butyloxyphenyl)fluoren-2-yl-]fluorene] (8) white solid.

Example 9 Poly(9,9-bis(9,9-dihexylfluoren-2-yl)-2,7-fluorenyl) (formula 2) synthesis

Equation 2

Wherein, n ₁ is an integer from 1 to 100000.

In a 500 ml Schrenk flask, 6 g (607 mmol) of compound (2) was dissolved in 66 ml of toluene degassed with nitrogen, and then kept under nitrogen atmosphere. Under nitrogen conditions, 3.576 grams (12.74 millimoles, 2.1 equivalents) of Ni(COD) ₂ , 1.392 grams (12.74 millimoles, 2.1 equivalents) of 1,4-cyclooctadiene (COD), 2.010 grams ( 12.74 millimoles, 2.1 equivalents) bipyridine was added in the Schrenk flask, 33 milliliters of toluene and 33 milliliters of N, N-dimethylformamide (N, N-Dimethylformamide, DMF) were added by nitrogen degassing, and then at 80 ° C Stir for 30 minutes. Add the prepared monomer solution into the reaction vessel and react for 24 hours. The resulting reaction solution was mixed with 2 ml of bromobenzene, and reacted for 24 hours to terminate the reaction. Then, the reaction solution was added to 1500 ml of a solution of hydrochloric acid (35% by weight): acetone: ethanol = 1:1:1 to remove unreacted catalyst and precipitate a polymer. The polymer was filtered and dissolved in chloroform, then filtered through celite to remove residual catalyst. Concentrate, reprecipitate in methanol, and wash with Soxlet for 24 hours. The yield was 69%, the weight average molecular weight Mw=180000, the number average molecular weight Mn=58000, and the polydispersity (polydispersity, PDI)=3.1.

4 and 5 show the ¹ H-NMR spectra of the monomer represented by compound (2) and the electroluminescent polymer represented by formula 2, respectively. As can be seen from these figures, the structures of the above monomers and polymers correspond to each other. Fig. 6 represents the photoluminescence (PL) spectrum of the electroluminescent polymer shown in formula 2 respectively in chloroform solution and film, wherein the highest peak of the photoluminescence (PL) spectrum in chloroform solution is at 418 nanometers, Corresponding to the blue emission region, the shoulder peak is at 442 nm. The highest peak of the photoluminescence (PL) spectrum on the film is at 427 nm, corresponding to the blue emission region, with a shoulder peak at 448 nm. Furthermore, no excimer peak, which is generally observed around 530 nm in the photoluminescence (PL) spectrum on the polyfluorene-based film, was observed in the present invention. Therefore, it could be confirmed that the compound of the present invention can be used as a material with high luminous efficiency.

Example 10

Synthesis of polymer (l ₁ :m ₁ =95:5) shown in formula 3

Equation 3

Wherein, l ₁ is an integer from 1 to 100,000, and m ₁ is an integer from 1 to 100,000.

This polymer was prepared using the same method as in Example 3, except that 95% of compound (2) and 5% of 4,4-dibromotriphenylamine were used as monomers. Weight average molecular weight Mw=165000, number average molecular weight Mn=61000, polydispersity=2.7.

Example 11

Synthesis of the polymer shown in formula 3 (l ₁ :m ₁ =90:10)

This polymer was prepared using the same method as in Example 3, except that 90% of compound (2) and 10% of 4,4-dibromotriphenylamine were used as monomers. Weight average molecular weight Mw=162000, number average molecular weight Mn=56000, polydispersity=2.9.

Example 12

Synthesis of the polymer shown in formula 3 (l ₁ :m ₁ =85:15)

This polymer was prepared using the same method as in Example 3, except that 85% of compound (2) and 15% of 4,4-dibromotriphenylamine were used as monomers. Weight average molecular weight Mw = 157000, number average molecular weight Mn = 60,000, polydispersity = 2.6.

Example 13

The synthesis of polymkeric substance shown in formula 4

Equation 4

Wherein, l ₂ is an integer from 1 to 100,000, and m ₂ is an integer from 1 to 100,000.

0.55 g of compound (8), 0.38 g of 9,9-bis(4-octylphenyl)fluorene-2,7-ethylene glycol diborate and 0.075 g of N,N-bis(4-bromophenyl) -N,N-bis(4-methoxyphenyl)-[1,1-biphenyl]-4,4-diamine was dissolved in 10 ml of toluene, 2.5 ml of water and 0.55 g of K ₃ PO were added to it _4. 0.02 g of tridecanoyl methylammonium chloride, then bubbled with nitrogen for 30 minutes. 0.01 g of tetrakis(triphenylphosphine)palladium(0) was added to the reaction mixture, followed by reaction at 89° C. for 24 hours. The resulting reaction solution was cooled to room temperature, and precipitated in 200 ml of methanol to filter the polymer. The filtered polymer was then dissolved in chloroform and filtered through hypoacetylide to remove residual catalyst. Concentrate, reprecipitate in methanol, and wash with Soxhlet for 24 hours. The yield was 72%, the weight average molecular weight Mw=150000, the number average molecular weight Mn=63000, and the polydispersity=2.4.

FIG. 8 shows the photoluminescence (PL) spectra of the electroluminescent polymer represented by Formula 4 in chloroform solution and film, respectively. As shown in the figure, the highest peaks of the photoluminescence (PL) spectra in solution and on the film were observed around 556 nm corresponding to the blue luminescent region, respectively.

Comparative example 1

An electroluminescent polymer (weight average molecular weight _Mw = 180000) having the following repeating unit was synthesized according to the method disclosed in WO 02/077060.

Embodiment 14-18 and comparative example 2

Fabrication of Electroluminescent Devices

Indium tin oxide (ITO) electrodes are formed on a glass substrate. The polymers for electroluminescent devices given in Table 1 below were then spin-coated on the ITO electrodes to form a light-emitting layer with a thickness of 600-1500 Angstroms (A). Al: Li was vacuum-deposited on the light-emitting layer to form an aluminum-lithium electrode with a thickness of 100-1200 Angstroms (A), so as to prepare an organic electroluminescent device, and then measure the light-emitting characteristics. The results are shown in Table 1 below.

Table 1 Example number luminous layer Driving Voltage (Volts) _ELλmax (nm) Maximum brightness (candela/square meter) Maximum efficiency (cd/A) Color coordinates (x, y) External Quantum Efficiency (%) 14 Example 9 7.1 426,447 467 0.716 0.160, 0.080 1.18 15 Example 10 7.0 443 693 1.45 0.160, 0.090 1.94 16 Example 11 6.5 439 740 1.08 0.159, 0.093 1.44 17 Example 12 6.5 439 864 0.88 0.159, 0.096 1.16 18 Example 13 6.0 455 720 0.64 0.160, 0.150 0.58 Comparative example 2 Comparative example 1 7.0 427,450 206 0.03 0.165, 0.097 0.04

Fig. 7 shows the electroluminescent spectrum obtained by the electroluminescent device (Example 14) using the electroluminescent polymer shown in formula 2, with the highest peak at 426 nm and 447 nm corresponding to the blue light emitting region. shoulder peak. Such a narrow wavelength band results in high color purity, and the peak of excimer atoms generally observed around 530 nm in the field emission spectrum of polyfluorene-based polymers is not observed in the present invention. Therefore, it can be found that the polymer compound used is a material with high luminous efficiency. Fig. 9 shows the electroluminescent spectrum obtained by the electroluminescent device (Example 18) using the electroluminescent polymer shown in formula 4, has the highest peak at 455 nm, and exhibits a high peak due to a narrow wavelength band. color purity.

In the above table, the results of Example 14 show the characteristics of the electroluminescent device prepared using the light-emitting layer made of the compound of Example 9, which was significantly higher than the characteristics of other polyfluorene-based polymers. The properties of the light emitting device were surprisingly excellent. In particular, the above-mentioned device with x=0.160 and y=0.080 in the color coordinate system has a color coordinate system that basically conforms to the standard blue color of the National Television Standards Committee (NTSC). In addition, the external quantum efficiency of 1.18% is considered to be the highest value among homopolyfluorenes known so far. For Example 15, Example 16, Example 17, and Example 18 using the amine Ar moiety of Formula 1, the driving initial voltage showed a decrease. Especially in Example 15 it can be seen that the quantum efficiency is significantly improved. This is because the structure of the substituent is similar to that of the main chain due to the introduction of the fluorenyl group as the main substituent, resulting in a random arrangement between the main chain and the substituent. In addition, aggregation and intermolecular excimer formation caused by substituents are suppressed, thereby avoiding aggregation and/or excimer formation, which are considered to be the biggest problems in the field of polyfluorene-based polymers. Intramolecular or intermolecular energy transfer from substituents with short wavelengths to the main chain can also be achieved. By substituting the fluorenyl group at the 9-position of fluorene as the main chain, the rotational and electronic vibrational modes are suppressed to thoroughly reduce non-radiative attenuation. Therefore, the organic electroluminescent polymer of the present invention has high luminous efficiency, and the organic electroluminescent device using the polymer has high color purity, high luminosity and high efficiency. Therefore, the electroluminescent polymer of the present invention is suitable for commercial use of electroluminescent devices.

Industrial Applicability

As described above, the present invention provides an organic electroluminescent polymer having 9,9-bis(fluorenyl)-2,7-fluorenyl units and an organic electroluminescent device prepared using the polymer. The electroluminescent polymer of the present invention has excellent thermal stability, high luminous efficiency and high solubility, and functions to minimize molecular interactions. Moreover, the above-mentioned polymers can avoid the disadvantages of conventional polyfluorene-based polymers, and can be used as host materials for blue, green and red luminescence of electroluminescence devices, thereby exhibiting excellent luminescence characteristics.

Although the preferred embodiment of the invention has been given for the purpose of description, those skilled in the art will appreciate that various modifications can be made without departing from the scope and spirit of the invention as disclosed in the appended claims. Add and replace.

Claims (12)

1. An organic electroluminescent polymer with 9,9-bis(fluorenyl)-2,7-fluorenyl units, the organic electroluminescent polymer is shown in formula 1 below: Formula 1 Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each is a linear or branched chain alkyl group of 1-20 carbon atoms; Or an aryl group substituted by at least one substituent in the group consisting of branched alkyl and alkoxy; having at least one heterogeneous group selected from the group consisting of F, S, N, O, P and Si straight-chain or branched-chain alkyl of 1-20 carbon atoms; selected from the group consisting of straight-chain or branched-chain alkyl and alkoxy of 1-20 carbon atoms containing at least one heteroatom At least one substituent substituted aryl group, the heteroatom is selected from the group consisting of F, S, N, O, P and Si; a heterocyclic part having 2-24 carbon atoms, unsubstituted or composed of An aryl group substituted by at least one substituent selected from the group consisting of straight-chain or branched alkyl and alkoxy groups of 1-20 carbon atoms; An aryl group substituted by at least one substituent selected from the group consisting of linear or branched chain alkyl and alkoxy groups of 1 to 20 carbon atoms containing at least one heteroatom selected from F, In the group consisting of S, N, O, P and Si; substituted or unsubstituted trialkylsilyl groups of 3-40 carbon atoms; substituted or unsubstituted arylsilyl groups of 3-40 carbon atoms substituted or unsubstituted carbazolyl of 12-60 carbon atoms; substituted or unsubstituted phenothiazinyl of 6-60 carbon atoms; or substituted or unsubstituted arylamine of 6-60 carbon atoms base; R ₅ , R ₆ , R ₇ and R ₈ are the same or different, and each is a straight-chain or branched chain alkyl or alkoxy group with 1-20 carbon atoms in hydrogen; unsubstituted or selected from 1-20 carbon atoms An aryl group substituted by at least one substituent in the group consisting of linear or branched alkyl and alkoxy; having at least one substituent selected from the group consisting of F, S, N, O, P and Si A straight-chain or branched chain alkyl or alkoxy group of 1-20 carbon atoms containing at least one heteroatom; An aryl group substituted by at least one substituent in the group consisting of radicals, the heteroatoms being selected from the group consisting of F, S, N, O, P and Si; a heterocyclic ring having 2-24 carbon atoms Partial, unsubstituted or aryl group substituted with at least one substituent selected from the group consisting of linear or branched alkyl and alkoxy groups of 1 to 20 carbon atoms; having 2 to 24 carbon atoms Aryl group substituted by at least one substituent selected from the group consisting of straight-chain or branched-chain alkyl and alkoxy groups of 1-20 carbon atoms containing at least one heteroatom in the heterocyclic part of The heteroatoms are selected from the group consisting of F, S, N, O, P and Si; substituted or unsubstituted trialkylsilyl groups with 3-40 carbon atoms; substituted or unsubstituted 3-40 Arylsilyl of carbon atoms; substituted or unsubstituted carbazolyl of 12-60 carbon atoms; substituted or unsubstituted phenothiazinyl of 6-60 carbon atoms; or substituted or unsubstituted 6- Arylamino group with 60 carbon atoms; a, b, c and d are the same or different, each being an integer from 1 to 3; Ar is selected from the group consisting of substituted or unsubstituted aromatic moieties of 6-60 carbon atoms, substituted or unsubstituted heteroaromatic moieties of 2-60 carbon atoms, and combinations thereof; l is an integer of 1 to 100,000, m is an integer of 0 to 100,000, and n is an integer of 1 to 100,000. 2. The organic electroluminescent polymer according to claim 1, wherein said R ₁ , R ₂ , R ₃ and R ₄ are respectively selected from the following group:

3. The organic electroluminescent polymer according to claim 1, wherein said _R5 and _R6 are respectively selected from the following groups:

Wherein said R ₉ and R ₁₀ are the same or different, and are respectively linear or branched chain alkyl groups with 1-20 carbon atoms; R ₁₁ is hydrogen, or a linear or branched alkyl, alkoxy or trialkylsilyl group of 1-20 carbon atoms; R ₁₂ and R ₁₃ are the same or different, and are respectively linear or branched chain alkyl groups of 1-20 carbon atoms; R ₁₄ , R ₁₅ and R ₁₆ are the same or different, and are respectively straight-chain or branched-chain alkyl or alkoxy groups of 1-20 carbon atoms, or unsubstituted or selected from straight-chain groups of 1-20 carbon atoms Or an aryl group substituted by at least one substituent in the group consisting of branched alkyl and alkoxy; R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are the same or different, and are hydrogen, straight-chain or branched-chain alkyl or alkoxy of 1-20 carbon atoms, or unsubstituted or composed of An aryl group substituted by at least one substituent selected from the group consisting of straight-chain or branched-chain alkyl and alkoxy groups of 1-20 carbon atoms; X is O or S; Y and Z are N; and a is an integer of 1 to 3; 4. The organic electroluminescent polymer according to claim 1, wherein said _R7 and _R8 are respectively selected from the following groups: 5. The organic electroluminescent polymer according to claim 1, wherein said Ar is selected from the group consisting of: (i) a substituted or unsubstituted arylene group of 6-60 carbon atoms; (ii) a substituted or unsubstituted heterocyclic arylene group of 2-60 carbon atoms, wherein the aromatic ring contains at least one heteroatom selected from the group consisting of N, S, P, O and Si; (iii) substituted or unsubstituted arylene vinylene groups of 6-60 carbon atoms; (iv) substituted or unsubstituted arylamino groups of 6-60 carbon atoms; (v) substituted or unsubstituted carbazolyl of 12-60 carbon atoms; and (vi) combinations thereof, Wherein Ar may comprise a straight chain or branched chain alkyl or alkoxy group selected from 1-20 carbon atoms; An aryl group substituted with at least one substituent in the group consisting of; a substituent in the group consisting of cyano and silyl. 6. The organic electroluminescent polymer according to claim 1, wherein the ratio of l to m is 5:95 to 95:5. 7. The organic electroluminescent polymer according to claim 5, wherein when the Ar is a substituted or unsubstituted aromatic amino group with 6-60 carbon atoms, the amount of Ar in the electroluminescent polymer The content is 5-15 mol%. 8. The organic electroluminescent polymer according to claim 1, wherein the organic electroluminescent polymer is represented by the following formula 2:

Equation 2 Where n is an integer from 1 to 100000. 9. The organic electroluminescent polymer according to claim 1, wherein the organic electroluminescent polymer is represented by the following formula 3:

Equation 3 Wherein l ₁ is an integer from 1 to 100000, and m ₁ is an integer from 1 to 100000. 10. The organic electroluminescent polymer according to claim 1, wherein the organic electroluminescent polymer is represented by the following formula 4:

Equation 4 Wherein l ₂ is an integer from 1 to 100000, and m ₂ is an integer from 1 to 100000. 11. An organic electroluminescence device having at least one layer comprising the polymer according to claim 1 between the anode and the cathode, wherein said layer is a hole transport layer, a light emitting layer, an electron transport layer or hole blocking layer. 12. The organic electroluminescent device according to claim 11, wherein the organic electroluminescent device comprises the following structure: anode/luminescent layer/cathode, anode/hole transport layer/luminescent layer/cathode, or anode/ Hole transport layer/light emitting layer/electron transport layer/cathode.

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