CN111278892A

CN111278892A - Polymer, mixture, composition containing amido bond group and application thereof

Info

Publication number: CN111278892A
Application number: CN201880069942.1A
Authority: CN
Inventors: 潘君友; 杨曦; 温华文
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2017-12-28
Filing date: 2018-12-17
Publication date: 2020-06-12
Anticipated expiration: 2038-12-17
Also published as: WO2019128762A1; CN111278892B

Abstract

The invention provides an amide bond group-containing polymer, a mixture containing the same, a composition containing the same, an organic electronic device containing the same and application of the organic electronic device. The polymer comprises a main chain structure connected by amide bonds and functionalized side chain groups; the polymer further comprises crosslinkable groups, and the polymer is crosslinked under a heating condition to form an insoluble and infusible polymer film, has excellent solvent resistance, and is suitable for manufacturing complex multilayer organic electronic devices through solution processing. The invention also relates to the application of the polymer in photoelectric devices such as organic field effect transistors, organic light emitting diodes, polymer solar cells, perovskite solar cells and the like.

Description

Polymer, mixture, composition containing amido bond group and application thereof

The present application claims priority from the chinese patent office filed on 28/12/2017, entitled "amide bond group-containing polymers and their use in organic electronic devices" under the invention of application number 201711461881.7, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to a polymer, a mixture, a composition and an application thereof.

Background

Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the versatility of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

In order to realize an efficient organic electroluminescent device, in addition to the development of a high-performance light emitting material, efficient injection of electrons and holes from a cathode and an anode, respectively, is a key among them. At present, most of transmission materials are small molecular materials and are suitable for preparing evaporation type OLED. Multilayer and complex high-efficiency OLED devices are easily prepared by a vacuum evaporation method, but the production cost is high, the time is consumed, and the material utilization rate is not high; especially, in the RGB side-by-side technology, it is difficult to realize the production of large-sized displays because of the use of a precision metal mask (FMM). In contrast, solution processing OLEDs can be used to fabricate large-area, flexible devices by inexpensive solution processing methods such as inkjet printing and printing, and have a wide application prospect and commercial value.

Because general polymer photoelectric materials have similar intermiscibility, that is, polymer luminescent materials, hole injection/transport materials and electron injection/transport materials have good solubility in solvents such as toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene and tetrahydrofuran, the problems of interface intermiscibility, interface erosion and the like exist when a multilayer and complex polymer light-emitting diode is prepared by a solution processing method. In order to solve the problem of interface erosion in solution processing, a cross-linking method is adopted at present, namely, a cross-linkable polymer photoelectric material is developed, the material has excellent solubility before cross-linking, a film can be formed by adopting the solution processing method, and then cross-linking groups of polymer side chains are initiated to mutually perform chemical reaction under the conditions of illumination, heat and the like to form an insoluble and infusible three-dimensional interpenetrating network polymer, so that the material has excellent solvent resistance and is convenient for the subsequent solution processing preparation of a functional layer (J.Mater.chem.2008,18,4495). However, the performance of solution processed OLEDs based on crosslinked polymers of these crosslinking groups has yet to be improved. Firstly, the existing crosslinkable polymers are all conjugated high polymers, the three-linear-state energy level of the polymers is lower, and the polymers cannot play a good exciton blocking role when used for phosphorescence green light, so that the efficiency is reduced; secondly, the stability of the existing crosslinkable polymer is limited, which causes the low service life of the OLED device.

Therefore, new high-performance crosslinkable high polymer charge transport materials need to be developed.

Disclosure of Invention

Based on the above, there is a need to provide a polymer, a mixture, a composition containing an amido bond group and applications thereof, so as to solve the problems of low triplet state and poor stability of the existing conjugated high polymer transport material and improve the device performance.

The technical scheme of the invention is as follows:

a polymer of the general formula (I):

wherein:

o, p is the number of repetitions of the repeating unit and is an integer greater than or equal to 1;

Ar¹and Ar²Each independently selected from aromatic, heteroaromatic or heteroaromatic groups having 5 to 50 ring atoms, said aromatic, heteroaromatic and non-aromatic groups optionally further being substituted by one or more R¹Substituent group substitution;

T¹and T²Each independently an amide group; and when there are a plurality of T¹A plurality of said T¹Same or different, when there are a plurality of T²A plurality of said T²The same or different;

a and b are each independently 0 or 1, and at least one of a and b is 1;

R¹selected from H, or D, or a linear alkyl group having 1 to 20C atoms, or an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched or cyclic group having 3 to 20C atomsAlkyl in the form of a cyclic or branched alkoxy group having 3 to 20C atoms or a branched or cyclic thioalkoxy group having 3 to 20C atoms, or is a substituted or unsubstituted silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, or a cyano group (-CN), an amido group (-C (═ O) N (R)₂) Haloformyl, formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

And when there are more than one R¹When a plurality of said R¹The same or different.

A mixture containing amide bond groups comprises at least one amide bond group-containing polymer and at least one other organic functional material, wherein the other organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.

A composition comprising at least one of the above amide bond group-containing polymers or the above amide bond group-containing mixtures, and at least one organic solvent.

An organic electronic device comprising at least one of the above amide bond group-containing polymers or mixtures of the above amide bond group-containing polymers.

The amide bond group-containing polymer has conjugated structural units, so that the polymer is endowed with rich optical and electrical properties. The polymer material is subjected to chemical reaction crosslinking under the heating condition to generate an insoluble and infusible interpenetrating network polymer film, has excellent solvent resistance, and is suitable for manufacturing complex multilayer organic electronic devices. Specifically, the method comprises the following steps:

(1) the polymer containing amido bond groups has abundant optical (photoluminescence, electroluminescence, photovoltaic effect and the like), electrical (semiconductor characteristics, carrier transmission characteristics and the like) and other performances, and has high polymer properties and good solubility and film-forming property. Under the heating condition, the polymer can perform chemical reaction to form a three-dimensional insoluble infusible interpenetrating network polymer film with excellent solvent resistance. When the complex multilayer photoelectric device is prepared, the solution processing characteristics of the polymer can be utilized, the polymer photoelectric device is prepared by the solution processing technologies such as ink-jet printing, silk-screen printing, spin coating and the like, and the polymer photoelectric device can be cross-linked among molecules to form an insoluble and infusible three-dimensional interpenetrating network polymer film, so that the polymer photoelectric device has excellent solvent resistance, and is beneficial to the solution processing of the multilayer polymer photoelectric device, particularly an organic electroluminescent device.

(2) Compared with the traditional conjugated polymer photoelectric material with alternately connected carbon-carbon single double bonds, the amide bond group-containing polymer of the invention has the advantages that the Lowest Unoccupied Molecular Orbital (LUMO) and the triplet state energy level (E) of the polymer are ensured due to the weaker conjugation capability of the amide group_T) The polymer has small influence with the increase of the polymerization degree, thereby being beneficial to limiting excitons in the light-emitting layer and being beneficial to the application in polymer photoelectric devices, particularly the application as a hole transport material.

Drawings

Fig. 1 is a schematic diagram of a preferred light-emitting device according to the present invention, in which 101 is a substrate, 102 is an anode, 103 is a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL), 104 is a light-emitting layer, 105 is an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 106 is a cathode.

Detailed Description

The invention provides an amido bond group-containing polymer and application thereof in an organic electronic device, and the invention is further detailed below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the embodiments of the present invention, the Host material, the Matrix material, the Host material, and the Matrix material have the same meaning and may be interchanged.

In the embodiments of the present invention, singlet states and singlet states have the same meaning and may be interchanged.

In the present embodiment, the triplet state and the triplet state have the same meaning and are interchangeable.

In the present invention, the composition and the printing ink, or ink, have the same meaning and may be interchanged.

Polymers, i.e., polymers, include homopolymers (homo polymers), copolymers (copolymers), and block copolymers. In addition, the term "polymer" as used herein also includes Dendrimers (dendromers), and reference is made to the synthesis and use of Dendrimers, Wiley-VCH Verlag GmbH & Co.KGaA,2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.

Conjugated polymer (conjugated polymer) is a polymer whose backbone is mainly composed of sp2 hybridized orbitals of C atoms, notable examples being: polyacetylene and poly (phenylene vinylene) in which the C atoms of the main chain may also be replaced by other non-C atoms and still be considered as conjugated polymers when sp2 hybridization in the main chain is interrupted by some natural defect. In the present invention, the conjugated polymer may include arylamines (aryl amines), aryl phosphines (aryl phosphines) and other heterocyclic aromatic hydrocarbons (heterocyclic aromatics), organic metal complexes (organometallic complexes) in the main chain.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_THOMO, LUMO play a key role. The determination of these energy levels is described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

Triplet energy level E of organic material_TCan be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian03W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E_TThe absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E_TIs based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO +1) is defined as the second lowest unoccupied orbital level, (LUMO +2) is the third lowest occupied orbital level, and so on.

The present invention provides a polymer of the general formula (I):

wherein:

a, b are each independently 0 or 1, and at least one of a and b is 1;

R¹selected from H, D, straight chain alkyl groups having 1 to 20C atoms, alkoxy groups having 1 to 20C atoms, thioalkoxy groups having 1 to 20C atoms, branched or cyclic alkyl groups having 3 to 20C atoms, branched or cyclic alkoxy groups having 3 to 20C atoms, branched or cyclic thioalkoxy groups having 3 to 20C atoms, substituted or unsubstituted silyl groups, keto groups having 1 to 20C atoms, alkoxycarbonyl groups having 2 to 20C atoms, aryloxycarbonyl groups having 7 to 20C atoms, cyano groups (-CN), amide groups (-C (═ O) N (R)₂) Haloformyl, formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

In a preferred embodiment, said T¹And T²Comprising a structure represented by the general formula (II):

wherein: r³Has the meaning of R¹。

In a more preferred embodiment, T is¹Or T²Containing one or more of the following structural formulae:

n1 represents an integer of 0 to 30.

In certain embodiments, the polymers according to the invention have a molecular weight Mw of 10000 g/mol or more, preferably 50000 g/mol or more, more preferably 100000 g/mol or more, still more preferably 150000 g/mol or more, most preferably 200000 g/mol or more.

In a preferred embodiment, Ar is¹And Ar²At each occurrence, each is independently selected from an aromatic group or a heteroaromatic group having 6 to 50 ring atoms; in a more preferred embodiment, Ar¹And Ar²At each occurrence, the aromatic or heteroaromatic groups are independently selected from aromatic groups or heteroaromatic groups with 6-45 ring atoms; in a highly preferred embodiment, Ar¹And Ar²At each occurrence, each independently selected from an aromatic group or a heteroaromatic group having 6 to 40 ring atoms; in the most preferred embodiment, Ar¹And Ar²At each occurrence, the aromatic or heteroaromatic groups are independently selected from aromatic groups or heteroaromatic groups with 6-30 ring atoms. Wherein one or more groups may be further substituted.

An aromatic ring system or aromatic group refers to an alkyl group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic ring systems or heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these ring species of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heteroaromatic groups are interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered aromatic groups for the purposes of this invention.

Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.

In some preferred embodiments, the polymer according to the invention, said Ar¹The pi-conjugated structure Unit with larger energy gap, also called Backbone Unit (Backbone Unit), is preferably more than or equal to 2.2 eV; more preferably at least 2.5 eV; more preferably ≧ 3.0 eV; most preferably ≧ 3.5 eV.

In a preferred embodiment, Ar is¹One or more combinations comprising the following structural groups:

wherein: when X is plural, plural of X are the same or different; x is CR⁴Or N;

when there are plural Y, plural of Y are the same or different; y is CR⁴R⁵、SiR⁴R⁵、NR⁴C (═ O), S, or O; r⁴、R⁵、R⁶Has the same meaning as R¹。

In certain preferred embodiments, the polymer according to the invention, wherein Ar¹Or Ar²And in multiple occurrences may be the same or different and are selected from the following structural groups: cyclic aromatic groups including benzene, biphenyl, triphenyl, benzo, fluorene, indofluorene and derivatives thereof; aromatic heterocyclic groups including triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzofurane, and benzofurane,Benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrolodipinene, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazines, indole, benzimidazole, indazole, indoxazine, bisbenzoxazoles, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazines, benzofuropyradine, furodipyridine, benzothiophenepyridine, thiendidine, thienopyridine, and unsellenopyridine, and the like.

In further preferred embodiments, the polymer is according to formula (I), wherein Ar¹Or Ar²In multiple occurrences, may be selected, identically or differently, from one or a combination of the following structural groups, which may be further optionally substituted:

wherein u is 1 or 2 or 3 or 4.

Generally, conjugated polymers comprise at least one backbone structural unit. The Backbone structural Unit is generally a pi-conjugated structural Unit with a larger energy gap, also called Backbone Unit, and can be selected from monocyclic or polycyclic aryl or heteroaryl. In the present invention, the conjugated polymer may contain two or more main chain structural units. Generally, the content of the main chain structural unit is not less than 40 mol%, preferably not less than 50 mol%, more preferably not less than 55 mol%, most preferably not less than 60 mol%.

In a preferred embodiment, the polymers according to the invention, wherein Ar is¹Is a high polymer main chain structural unit selected from benzene, biphenyl, triphenyl, benzo, fluorene, indofluorene, carbazole, indocarbazole, dibenzothiaole, dithienocyclopentadiene, dithienothiaole, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran, benzothiophene, benzoselenophene and derivatives thereof.

In a most preferred embodiment, Ar is¹Selected from the group consisting of benzene, Biphenylene (Biphenylene), naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9, 10-dihydrophenanthrene, fluorene, bifluorene, spirobifluorene, paraphenylenevinylene, retro-indenofluorene, cis-indenofluorene, dibenzo-indenofluorene, indenonaphthalene and derivatives thereof.

In certain preferred embodiments, the polymers of the present invention have hole transport properties.

In certain preferred embodiments, the polymer according to the invention, Ar²A pi-conjugated structural unit with a smaller energy gap, preferably less than or equal to 3.5 eV; more preferably less than or equal to 3.2 eV; most preferably less than or equal to 3.0 eV; the polymer contains a conjugated structure with a smaller energy gap, so that the polymer can generate charges more easily under the action of an electric field.

In a preferred embodiment, the polymers according to the invention, wherein Ar is²Preferred hole transporting units are selected from the group consisting of aromatic amines, triphenylamines, naphthylamines, thiophenes, carbazoles, dibenzothiophenes, dithienocyclopentadienes, dithienothioles, dibenzoselenophenes, furans, thiophenes, benzofurans, benzothiophenes, benzoselenophenes, carbazoles, indolocarbazoles and derivatives thereof.

In another preferred embodiment, Ar²Has a structure represented by chemical formula 1:

chemical formula 1

Wherein Ar1, Ar2 and Ar3 can independently select the same or different forms when appearing for multiple times

Ar1 is selected from single bond, mononuclear aryl, polynuclear aryl, mononuclear heteroaryl or polynuclear heteroaryl, which aryl or heteroaryl may be substituted by other side chains.

Ar2 is selected from the group consisting of mononuclear aryl, polynuclear aryl, mononuclear heteroaryl or polynuclear heteroaryl, which aryl or heteroaryl may be substituted with other side chains.

Ar3 is selected from the group consisting of mononuclear aryl, polynuclear aryl, mononuclear heteroaryl or polynuclear heteroaryl, which aryl or heteroaryl may be substituted with other side chains. Ar3 may also be attached to the other moieties in formula 1 through a bridging group.

n is selected from 1,2,3,4, or 5.

The structural unit represented by chemical formula 1 is preferably chemical formula 2

Chemical formula 2

Wherein Ar4, Ar6, Ar7, Ar10, Ar11, Ar13 and Ar14 are defined as Ar2 in chemical formula 1,

ar5, Ar8, Ar9 and Ar12 are defined as Ar3 in the chemical formula 1.

Ar1-Ar14 in chemical formula 1 and chemical formula 2 are preferably selected from benzene (phenylene), naphthalene (naphthalene), anthracene (anthracene), fluorene (fluorene), spirobifluorene (spirobifluorene), indofluorene (indofluorene), phenanthrene (phenanthrene), thiophene (thiolene), pyrrole (pyrrole), carbazole (carbazole), binaphthyl (binaphhthhalene), dehydrophenoanthrene and the like.

Particularly preferred choices among the structural units represented by chemical formulas 1 and 2 are listed, wherein each of the compounds may be substituted with one or more substituents, and R is a substituent.

TABLE 1

R is selected from H, or D, or aliphatic alkane containing 1 to 10 carbon atoms, aromatic hydrocarbon, substituted or unsubstituted aromatic ring containing 5 to 10 ring atoms or heteroaromatic group. When a plurality of R's are present, the plurality of R's may be the same or different.

Further suitable units with hole transport properties correspond to hole transport materials, small molecule Hole Transport Materials (HTMs). Suitable HTM materials may be selected from compounds comprising the following structural units: phthalocyanines (phthalocyanines), porphyrins (porphyrines), amines (amines), aromatic amines, triphenylamines (triarylamines), thiophenes (thiophenes), polythiophenes (fused thiophenes), such as dithienothiophene and benzothiophene (dibenzothiphenes), pyrroles (pyrroles), anilines (anilines), carbazoles, indolizines (indolocarbazoles), and derivatives thereof.

In certain particularly preferred embodiments, Ar is²One or more combinations comprising the following structural groups:

wherein: ar (Ar)³-Ar¹¹Independently at each occurrence, is selected from an aromatic or heteroaromatic ring system of 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group of 5 to 40 ring atoms, or a non-aromatic group of 5 to 40 ring atoms, or a combination of these systems, wherein one or more of the groups may be further substituted;

preferably, Ar³-Ar¹¹Independently at each occurrence, is selected from an aromatic or heteroaromatic ring system of 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group of 5 to 20 ring atoms, or a non-aromatic group of 5 to 20 ring atoms, or a combination of these systems, wherein one or more of the groups may be further substituted;

in certain preferred embodiments, the polymers of the present invention have electron transport properties.

In certain more preferred embodiments, the polymer according to the present invention, wherein Ar is²Selected from units having electron transport properties, preferred electron transport units are selected from pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, and mixtures thereof,Pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazines, benzofurylpyridine, furodipyridine, benzothiodipyridine, thienodipyridine, benzoselenophenylpyridine and selenophenyldipyridine and derivatives thereof.

In principle, all electron transport materials ETM can be used as the cell having electron transport properties of the present invention. ETM is also sometimes referred to as an n-type organic semiconductor material. In principle, examples of suitable ETM materials are not particularly limited, and any metal complex or organic compound may be used as the ETM as long as they can transport electrons. Preferred organic ETM materials may be selected from tris (8-hydroxyquinoline) aluminum (AlQ3), Phenazine (Phenazine), Phenanthroline (Phenanthroline), Anthracene (Anthracene), Phenanthrene (Phenanthrene), Fluorene (Fluorene), Bifluorene (Bifluorene), spirobifluorene (Spiro-Bifluorene), p-Phenylene vinylene (Phenanthrene-vinylene), triazine (triazine), triazole (triazole), imidazole (imidazole), Pyrene (Pyrene), Perylene (Perylene), trans-Indenofluorene (trans-Indenofluorene), cis-Indenofluorene (cis-Indenofluorene), dibenzo-Indenofluorene (dibenzo), Indenonaphthalene (indolylene), benzo-xanthene (benzanthrene) and their derivatives.

On the other hand, the Ar having an electron transport property²Can be selected from groups having a backbone of any of the following general formulae:

wherein: t represents an integer of 1 to 20;

R⁷at each occurrence, independentlySelected from hydrogen, deuterium, halogen (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl;

X₁-X₈at each occurrence, is independently selected from CR⁸Or N, and at least one is N;

M¹、M²、M³each independently represents N (R)⁸)、C(R⁸)₂、Si(R⁸)₂、O、C＝N(R⁸)、C＝C(R⁸)₂、P(R⁸)、P(＝O)R⁸、S、S＝O、SO₂Or none; ar (Ar)¹²-Ar¹⁶Has the same meaning as Ar³；R⁸Has the same meaning as R¹。

In a particularly preferred embodiment, the polymers of the present invention contain crosslinkable groups; the crosslinkable group is preferably selected from linear or cyclic alkenyl groups, linear dienyl groups, alkynyl groups, alkenyloxy groups, dienyloxy groups, acrylic groups, glycidylalkyl groups, epoxybutanyl groups, silyl groups, cyclobutane groups.

In a most preferred embodiment, the crosslinkable group is selected from one of the following structures:

wherein the dotted line represents the position where the crosslinking monomer is bonded to other monomers or functional groups on the monomers in the polymer, and t1 represent integers of 0 or more.

Ar¹⁷Aromatic ring systems containing 5 to 40 ring atomsOr a heteroaromatic ring system;

R⁹～R¹¹at each occurrence, is independently selected from the group consisting of: H. d, F, CN, alkyl chain, fluoroalkyl chain, aromatic ring, aromatic heterocycle, amino, silicon base, germyl group, alkoxy group, aryloxy group, fluoroalkoxy group, siloxane, siloxy group, deuterated alkyl chain, deuterated partially fluorinated alkyl chain, deuterated aromatic ring, deuterated aromatic heterocycle, deuterated amino group, deuterated silicon base, deuterated germyl group, deuterated alkoxy group, deuterated aryloxy group, deuterated fluoroalkoxy group, deuterated siloxane, deuterated siloxy group, crosslinkable group. And adjacent R⁹、R¹⁰、R¹¹The rings which may be bonded to each other or to said groups form a mono-or polycyclic, aliphatic or aromatic ring system;

the crosslinkable groups may be present in the polymer in various forms. Preferably, the crosslinkable group substitutes each repeating unit on the polymer in the form of a substituent, such as the following formula:

wherein Q is a crosslinkable group as described above, Ar is a repeating unit on the polymer, and x is a mole fraction

In a preferred embodiment, the crosslinkable group is attached to Ar¹The above.

In another preferred embodiment, the crosslinkable group is attached at T¹Or T²The above.

In a most preferred embodiment, the crosslinkable group is attached to Ar²The above.

In certain embodiments, the mole fraction x of repeating units comprising the crosslinkable group is: 0.02. ltoreq. x.ltoreq.0.30, preferably 0.05. ltoreq. x.ltoreq.0.25, more preferably 0.08. ltoreq. x.ltoreq.0.20, most preferably 0.10. ltoreq. x.ltoreq.0.18.

In certain preferred embodiments, the polymer according to formula (I), Ar having hole transport properties²The molar number of (b) is yh, wherein 0.02. ltoreq. yh.ltoreq.0.30, preferably 0.05. ltoreq. yh.ltoreq.0.25, more preferably 0.08. ltoreq. yh.ltoreq.0.20, most preferably 0.10. ltoreq. yh.ltoreq.0.18.

In further embodiments, the polymer according to formula (I), Ar having electron transport properties²The number of moles of ye is 0.02 to 0.30, preferably 0.05 to 0.25, more preferably 0.08 to 0.20, most preferably 0.10 to 0.18.

In a preferred embodiment, the polymer | HOMO-1) -HOMO | of the present invention is 0.3eV, preferably 0.35eV, more preferably 0.4eV, still more preferably 0.45eV, and most preferably 0.5 eV. Where HOMO represents the highest occupied orbital of the polymer and HOMO-1 represents the second highest occupied orbital of the polymer.

In a preferred embodiment, the polymers according to the invention have a higher LUMO, preferably a LUMO of ≧ 2.7eV, more preferably ≧ 2.6eV, even more preferably ≧ 2.5eV, most preferably ≧ 2.4 eV.

In certain preferred embodiments, polymers according to the present invention have a lower HOMO, preferably a HOMO of less than or equal to-5.0 eV, more preferably less than or equal to-5.1 eV, and most preferably less than or equal to-5.2 eV.

In certain preferred embodiments, the polymers according to the invention have a relatively large triplet energy level E_TPreferably E_TMore preferably, the value is not less than 2.5eV, still more preferably not less than 2.6eV, and most preferably not less than 2.7 eV.

In a more preferred embodiment, the polymer according to the invention is a conjugated polymer.

In one embodiment, in the general formula (I), a is 1, b is 1, o is 1, and p is 1;

in one embodiment, the polymer has a structural unit represented by any one of the following general formulae (II-1) to (II-10):

wherein R is¹¹、R¹²And R¹³Is as defined for R³；

A is a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic group having 5 to 30 ring atoms;

l is absent, or is CH₂；

W is O or S;

0 < e <1, 0 < f <1, and e + f ═ 1.

In one embodiment, A in formulas (II-1) to (II-10) is selected from the following groups:

wherein Y is CR¹⁴R¹⁵、SiR¹⁴R¹⁵、NR¹⁴O, S or Se;

R¹⁴、R¹⁵each independently being H, C1-C20 alkyl, vinyl,

R¹¹Is H, C1-C20 alkyl, ethenyl, ethynyl,

When there are more than one R¹¹When a plurality of said R¹¹The same or different;

R¹²and R¹³Each independently selected from the group consisting of: H. C1-C20 alkyl, 3-10 membered cycloalkyl, phenyl or

When there are a plurality of said Rs¹²Or R¹³When a plurality of said R¹²Or R¹³The same or different.

In one embodiment, the polymer has a structural unit represented by the general formula (III-1)

R¹⁴、R¹⁵Each independently is H or C1-C10 alkyl;

R¹¹is H, C1-C20 alkyl or vinyl; when there are more than one R¹¹When a plurality of said R¹¹The same or different;

n is 1 or 2.

In one embodiment, the polymer has a structure represented by the general formula (III-2)

The R is¹⁶And R¹⁷Each independently selected from: r¹¹Is H, C1-C6 alkyl or vinyl, and the R is¹⁶And R¹⁷Are not identical.

Examples of polymers according to the invention are listed below, but are not limited to:

the invention also relates to a method for synthesizing polymers according to formula (I), wherein the reaction is carried out using starting materials containing reactive groups. The polymer can be obtained by polycondensation of at least one monomer containing a lactam or both an amine group and an acid group (including carboxylic acid, acid halide, etc.), or at least two monomers containing a diamine and a diacid group (including carboxylic acid, acid halide, etc.), respectively.

The polymer of the present invention may be a homopolymer or a copolymer. The copolymers may be random, alternating, block, comb or dendritic. The processes used to form these different structured polymers are well known in the art, such as the principles Of Polymerization, third edition, by George Odian (John Wiley & Sons, New York, NY, 1991); chemical Reactions of Natural and Synthetic Polymers by Lazer et al; and Chemical Reactions on Polymers (1988) by Benham and Kinstle.

The polymer according to formula (I) is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.

In a preferred embodiment, the glass transition temperature (Tg) of the above-mentioned high polymer is not less than 100 ℃, preferably not less than 120 ℃, more preferably not less than 140 ℃, still more preferably not less than 160 ℃, most preferably not less than 180 ℃.

In a preferred embodiment, the molecular weight distribution (PDI) of the polymer is preferably in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the above-mentioned polymer is preferably in the range of 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.

The invention also provides a mixture, which is characterized by comprising at least one polymer and at least another organic functional material, wherein the at least another organic functional material can be selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent material (Emitter), a main body material (Host) and an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In a preferred embodiment, the mixture comprises a polymer according to the invention and a fluorescent emitter (or singlet emitter). The polymers according to the invention can be used as hosts, where the fluorescent emitters are present in a proportion of < 15% by weight, preferably < 12% by weight, more preferably < 9% by weight, more preferably < 8% by weight, most preferably < 7% by weight.

In certain embodiments, the mixture comprises a polymer according to the present invention, and a TADF material.

In a further preferred embodiment, the mixture comprises a polymer according to the invention and a phosphorescent emitter (or triplet emitter). The polymers according to the invention can be used as hosts, where the phosphorescent emitters are present in a proportion of < 30% by weight, preferably < 25% by weight, more preferably < 20% by weight, most preferably < 18% by weight.

In further preferred embodiments, the mixture comprises a polymer according to the invention and an HTM material.

Some more detailed descriptions of singlet emitters, triplet emitters and TADF materials are provided below (but not limited thereto).

1. Singlet state luminophor (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. Hitherto, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019, KR 2006-0006760.

In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.

A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 position of pyrene.

Examples, also preferred, of singlet emitters based on vinylamines and arylamines can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557A 1, CN 1583691A, JP 08053397A, US 6251531B 1, US 2006/210830A, EP 1957606A 1 and US 2008/0113101A 1 and the entire contents of the patent documents listed above are hereby incorporated by reference.

An example of singlet emitters based on stilbene and its derivatives is US 5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Further preferred singlet emitters may be selected from fluorene based fused ring systems as disclosed in US2015333277a1, US2016099411a1, US2016204355a 1.

More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509a 1; triarylamine derivatives of pyrene, such as pyrene triarylamine derivatives containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having specific structures are disclosed in CN105085334A, CN 105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of anthracene, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene, such as 2,5,8, 11-tetra-t-butylperylene, indenopyrene, phenylene, such as (4,4 '-bis (9-ethyl-3-carbazolyl-vinyl) -1, 1' -biphenyl, diindenopyrene, decacycloalkene, coronene, fluorene, spirobifluorene, arylpyrene, such as U.S. 20060222886, aryleneethene, such as U.S. Pat. No. 5121029, U.S. Pat. No. 5,8803, cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) iminoboron compounds (US 2007/0092753 a1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some singlet emitter materials can be found in the patent documents US 20070252517A 1, US 4769292, US 6020078, US 2007/0252517A 1, US 2007/0252517A 1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the following table:

2. triplet Emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) u, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and u is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:

where M is a metal selected from the transition metals or the lanthanides or actinides, particularly preferably Ir, Pt, Au;

Ar₁each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)₂Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)₁And Ar₂Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q may be 0,1,2 or 3, preferably 2 or 3; p may be 0,1,2 or 3, preferably 1 or 0.

Examples of materials and their use for some triplet emitters can be found in WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, Baldo, Thompson et al. Nature 403, (2000), 750-and 753, US 2010099852A 2010099852, US 2010099852A 2010099852, Adachi. Appl. Phyt. Lett.78(2001), 1622-and 1624, J.Kido et al. Appl. Phys. Lett.65(1994), U.Kido.Phyt. 364, Chedo.657, US 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 3655, US 2010099852, US 2010099852, US 2010099852, WO 2012007088a1, WO2012007087a1, WO 2012007086a1, US 2008027220a1, WO 2011157339a1, CN 102282150a, WO 2009118087a1, WO 2013107487a1, WO 2013094620a1, WO 2013174471a1, WO 2014031977a1, WO 2014112450a1, WO 2014007565a1, WO 2014038456a1, WO 2014024131a1, WO 2014008982A1, WO2014023377a 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the following table:

3. thermally activated delayed fluorescence luminescent material (TADF):

the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials typically have a small singlet-triplet energy level difference (Δ E)_st) The triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in patent documents CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et. al. adv.mater, 21,2009,4802, Adachi, et. al. appl.phys.lett.,98,2011,083302, Adachi, et. al. appl.phys.lett, 101,2012,093306, Adachi, chem.comm.comm, 48,2012,11392, Adachi, et. nature. natronics, 6,2012,253, Adachi, et. nature,492,2012,234, Adachi, am.j.am.t., 48,2012,11392, Adachi, et. nature, adochi, et. phytol.27, Adachi, et. phytol.t.8, Adachi, adachi.t.t.t.J.38, adachi.t.7, adachi.8, adachi.t.t.t.t.7, adachi.t.t.t.7, adachi.7, adachi.t.t.t.t.t.t.t.t.7, adachi.7, adachi.t.t.7, adachi.7, adachi.t.k.t.t.t.t.t.t.t.t.7, Adachi, adachi.k.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.k.k.t.t.t.t.t.t.t.t.t.t.

It is another object of the present invention to provide a material solution for printing OLEDs.

In further embodiments, the polymers according to the invention have a solubility in toluene of > 5mg/ml, preferably > 7mg/ml, most preferably > 10mg/ml at 25 ℃.

According to one composition of the invention, the at least one organic solvent is chosen from aromatic or heteroaromatic, ester, aromatic ketone or ether, aliphatic ketone or ether, alicyclic or olefinic compound, or borate or phosphate compound, or a mixture of two or more solvents.

In a preferred embodiment, according to a composition of the invention, said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.

Examples of aromatic or heteroaromatic-based solvents suitable for the present invention include, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisoprene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisoprene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, 1, 2-dimethylquinoline, 2-benzoic acid, 2-isopropylquinoline, 2-benzoic acid, 2-ethyl benzoate, and the like;

examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other preferred embodiments, the at least one organic solvent may be chosen from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention comprises a polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent, examples of which include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

δ_d(dispersion force) of 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

δ_p(polar force) is 0.2 to 12.5MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2A range of (d);

δ_h(hydrogen bonding force) of 0.9 to 14.2MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

The invention also relates to the use of said composition as a printing ink for the production of organic electronic components, particularly preferably by printing or coating.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, screen printing and ink jet printing are preferred. Gravure printing, ink jet printing, will be used in the examples of the present invention. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvents and concentrations, viscosities, etc., reference is made to the Handbook of Print Media, technology and Production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

The method for preparing the organic electroluminescent device is characterized in that the formed functional layer has a thickness of 5nm to 1000 nm.

The invention further relates to an organic electronic device comprising at least one polymer or mixture as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain particularly preferred embodiments, the electroluminescent device, the electron transport layer or the hole transport layer, comprises a polymer or a mixture as described above.

The invention further comprises a process for the preparation of a functional layer comprising the polymer according to the invention in an organic electronic device, comprising at least the following steps:

the first step is as follows: dissolving the polymer in an organic solvent or a mixed solvent to prepare a solution;

the second step is that: applying the solution to a functional layer of a device by Printing or coating, wherein the Printing or coating can be selected from, but is not limited to, ink jet Printing, jet Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexographic Printing, rotary Printing, spray coating, brush coating or pad Printing, slit die coating, and the like;

the third step: the obtained film is subjected to heat treatment at a temperature of at least 100 ℃, and ultraviolet light can be optionally added to carry out crosslinking reaction, so that the film is cured.

Optional steps are as follows: and cleaning the film after crosslinking and curing by using an organic solvent to remove residual compounds which are not crosslinked and cured.

In certain embodiments, the resulting crosslinked cured film (after solvent washing) has a thickness of at least 50%, preferably at least 60%, more preferably at least 70%, and most preferably at least 85% of the film prior to crosslinking and curing.

In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.

The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

1. Synthesis of polymers

Example 1: synthesis of Polymer P1

Synthesis of intermediate 2

Dissolving Compound 1(7.03g, 10mmol) in 80ml acetic acid in a 250ml round bottom flask, adding 80ml fuming nitric acid and 20ml concentrated sulfuric acid dropwise, stirring, heating to 90 deg.C under nitrogen atmosphere, reacting for 15h, cooling the reaction product, pouring into ice water, extracting the product with dichloromethane, sequentially extracting the organic phase with NaHCO₃The saturated solution, saturated brine and water were washed, and the solvent was evaporated and dried to give a crude product, which was passed through a column chromatography to give intermediate 2 in a weight of 4.83g and a yield of 61%.

Synthesis of intermediate 3

Dissolving the intermediate 2(1.59g and 2mmol) in 50ml of ethanol under the protection of nitrogen, adding hydrazine monohydrate (1.02g and 20mmol) and palladium-carbon (0.1g (10% w/w)), stirring, refluxing for 2 hours, filtering after the reaction is finished, extracting the filtrate with dichloromethane, washing an organic phase with saturated brine and water, drying to obtain a crude product, and performing chromatography to obtain the intermediate 3 with the weight of 1.24g and the yield of 85%.

Synthesis of intermediate 4

Aniline (0.93g,0.01mol) and ethyl 4-bromobenzoate (4.58g,0.02mol), sodium tert-butoxide (8.45g,0.088mol), the catalyst bis (dibenzylideneacetone) palladium (1.27g,0.0022mol) were added to a two-necked flask, dried toluene was used as the reaction solvent, nitrogen was bubbled through for 30min, and then 13ml of tri-tert-butylphosphine was added. The reaction progress is tracked, water is added to stop the reaction after the reaction is finished, ethyl acetate is used for extraction, the organic phase is subjected to rotary evaporation to remove the solvent, silica gel is added to mix with powder, the sample is loaded on a silica gel column, and the product intermediate 4 with the weight of 2.95g and the yield of 76% is obtained.

Synthesis of intermediate 5

Under nitrogen protection, 5ml (64mmol) of freshly distilled DMF was added to a 50ml three-necked flask. 6ml (64mmol) of phosphorus oxychloride was slowly added dropwise in an ice bath and stirred rapidly. After the phosphorus oxychloride had been added dropwise, a solution of intermediate 4(8.95g, 23mmol) in 55ml of DMF was slowly added dropwise. After the dripping is finished, the mixture is heated to 35 to 40 ℃ under the protection of nitrogen and stirred overnight. The resulting solution was poured into 200ml of water. After filtration, the filter cake obtained was recrystallized from ethanol to give intermediate 5, 9.20g in weight, 96% yield.

Synthesis of intermediate 6

In a dry 250mL two-necked flask, potassium tert-butoxide (2.24g, 20mmol), methyltriphenylphosphonium bromide (4.28g, 12mmol) and 40mL of freshly evaporated tetrahydrofuran were placed under an ice bath and nitrogen blanket. After stirring for half an hour, a solution of intermediate 5(4.17g, 10mmol) in 20ml of tetrahydrofuran was added, after which time the temperature was slowly raised to room temperature and stirring was continued for 4 hours under nitrogen. After adding water to quench the reaction, the mixture is extracted with petroleum ether and dried over anhydrous sodium sulfate. Column chromatography with petroleum ether as developing solvent gave intermediate 6, 2.49g in weight, 60% yield.

Synthesis of intermediate 7

Intermediate 6(0.415g, 1mmol) was dissolved in 6ml of methanol and 7ml of (6M) aqueous sodium hydroxide was added, after 2h reaction at room temperature, hydrochloric acid was added to pH 1, extraction was performed with ethyl acetate and washing was performed with saturated brine, after drying, the solvent was removed in vacuo, the resulting solid was dissolved in 20ml of anhydrous dichloromethane, 0.34ml (4mmol) of oxalyl chloride was added under nitrogen protection and a catalytic amount of DMF was added dropwise, reaction was stirred at room temperature for 2h, and the solvent was removed in vacuo to give intermediate 7, weighing 0.18g, yield 46%.

Synthesis of Polymer P1

Intermediate 3(733mg, 1mmol) and intermediate 7(396mg, 1mmol) were added to a 25mL reaction flask under nitrogen and dissolved in 10mL DMAc, the reaction was stirred at room temperature for 12h, the solution was poured into a large volume of water, the precipitate was filtered and washed with methanol and acetone, and dried under vacuum to give polymer P1, weight 898 mg.

Example 2: synthesis of Polymer P2

Synthesis of intermediate 8

4-tert-butylaniline (1.49g,0.01mol) and ethyl 4-bromobenzoate (4.58g,0.02mol), sodium tert-butoxide (8.45g,0.088mol), the catalyst bis (dibenzylideneacetone) palladium (1.27g,0.0022mol) were added to a two-necked flask, dried toluene was used as the reaction solvent, nitrogen was bubbled through for 30min, and then 13ml of tri-tert-butylphosphine was injected. The reaction progress was followed, after the reaction was completed, water was added to terminate the reaction, ethyl acetate was used for extraction, the organic phase was rotary evaporated to remove the solvent, silica gel was added to mix with powder and the sample was passed through a silica gel column to obtain the product intermediate 8, 3.69g in weight, 83% yield.

Synthesis of intermediate 9

Intermediate 8(0.445g, 1mmol) was dissolved in 6ml of methanol and 7ml of (6M) aqueous sodium hydroxide was added, after reaction for 2h at room temperature, hydrochloric acid was added to pH 1, extraction was performed with ethyl acetate and washing was performed with saturated brine, the solvent was removed after drying, the obtained solid was dissolved in 20ml of anhydrous dichloromethane, oxalyl chloride (0.34ml, 4mmol) was added under nitrogen protection, and a catalytic amount of DMF was added dropwise, reaction was stirred at room temperature for 2h, and the solvent was removed under vacuum to give intermediate 9, 0.22g in weight, 51% yield.

Synthesis of Polymer P2

Intermediate 3(733mg, 1mmol), intermediate 7(119mg, 0.3mmol) and intermediate 9(298mg, 0.7mmol) were added to a 25mL reaction flask under nitrogen and dissolved in 10mL DMAc, the reaction was stirred at room temperature for 12h, the solution was poured into a large volume of water, the precipitate was filtered, washed with methanol and acetone, and dried under vacuum to give polymer P2, weighing 761 mg.

Example 3: synthesis of Polymer P3

Under the protection of nitrogen, compound a (370mg, 1mmol) and compound b (141mg, 1mmol) were dissolved in anhydrous dichloromethane, and 22ml of 1-hydroxybenzotriazole solution (1M, DMF/CH) was added under ice bath₂Cl₂1:1) and 20ml dicyclohexylcarbodiimide solution (1M, CH)₂Cl₂) The reaction was stirred at room temperature for 2 days, the precipitate was filtered, the filtrate was dried in vacuo, the solid was dissolved in dichloromethane and 10% NaHCO₃The aqueous solution was washed and dried to give polymer P3 weighing 327 mg.

2. Energy level structure of compound

The organic small molecule energy structure can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian03W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet).

For conjugated polymers, the energy structure of the polymer can be obtained by calculating the trimer. For example, compounds P1, trimers M1-M2-M1 and/or M2-M1-M2, obtained by polymerization of monomers M1 and M2 as shown below, in which the alkyl chains are each substituted with a methyl group, were used to calculate the energy levels.

Trimer M1-M2-M1:

trimer M2-M1-M2:

the HOMO and LUMO energy levels calculated above were calculated according to the following calibration formula, and S1 and T1 were used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian 09W in eV. The results are shown in table one, where Δ HOMO ═ HOMO- (HOMO-1):

preparation method of OLED device

Wherein H1 is a co-host material, and the synthesis thereof refers to Chinese patent with application number CN 201510889328.8; h2 is a co-host material, the synthesis of which is described in patent WO201034125a 1; e1 is a phosphorescent guest, the synthesis of which is referred to patents CN 102668152; comp a to Comp C and Poly-TFB are comparative materials for a device HTL, wherein the synthesis of Comp a, Comp B and Comp C is similar to the compounds of similar structure of this patent; Poly-TFB (CAS:223569-31-1) was purchased from Lumtec.

The device structure of the OLED device (OLED-Ref) is as follows: ITO/PEDOT PSS (80nm)/Poly-TFB (20 nm)/EML/cathode; the OLED device (OLED-Ref) is prepared by the following steps:

1) cleaning of an ITO transparent electrode (anode) glass substrate: carrying out ultrasonic treatment for 30 minutes by using an aqueous solution of 5% Decon90 cleaning solution, then carrying out ultrasonic cleaning for several times by using deionized water, then carrying out ultrasonic cleaning by using isopropanol, and carrying out nitrogen blow-drying; processing for 5 minutes under oxygen plasma to clean the ITO surface and improve the work function of an ITO electrode;

2) preparation of HIL and HTL by spin coating PEDOT: PSS (Clevios) on a glass substrate treated with oxygen plasma^TMPEDOT, PSS Al4083), obtaining a film with the thickness of 80nm, and annealing the film for 20 minutes in air at 150 ℃ after the spin coating is finished; then spin-coating on a PEDOT: PSS layer to obtain a 20nm Poly-TFB film (5mg/mL toluene solution), followed by treatment on a hot plate at 180 ℃ for 60 minutes;

3) preparing a luminescent layer by mixing H1, H2 and E1 according to the weight ratio of 40: 40: 20 in toluene at a concentration of 20mg/mL, was spin-coated in a nitrogen glove box to give a 60nm film, which was then annealed at 120 ℃ for 10 minutes.

4) And (3) preparing a cathode, namely putting the spin-coated device into a vacuum evaporation cavity, and sequentially evaporating 2nm barium and 100nm aluminum to complete the light-emitting device.

5) All devices were encapsulated in a nitrogen glove box with uv cured resin plus glass cover plate.

The other OLED devices (OLED-1 to OLED-3 and OLED-A to OLED-C) were prepared as above, but in the preparation of the HTL layer, P1 to P3 and Comp A to Comp C were used to replace Poly-TFB, respectively, and after curing by crosslinking, rinsed twice with toluene and the film thickness was measured.

The current-voltage characteristics, the luminous intensity and the external quantum efficiency of the device were measured by a Keithley236 current-voltage measurement system and a calibrated silicon photodiode.

	HTL thickness (nm)	Efficiency (cd/A) @1000nits relative to OLED-Ref
OLED-Ref	20	1
OLED-1	20	1.33
OLED-2	20	1.57
OLED-3	20	1.45
OLED-A	20	1.02
OLED-B	20	0.85
OLED-C	20	0.94

The polymers according to the invention have a greatly improved performance, in particular efficiency, when used in HTLs compared to other comparative devices. This is probably because of two reasons, i.e., the polymer HTM containing amide bond groups according to the present invention has a higher triplet energy level, thereby having a better barrier effect on the triplet state; secondly, the polymer containing amido bond groups has better solubility and is suitable for solution processing, and the insolubility after crosslinking and curing is also suitable for subsequent processing.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims

An amide bond group-containing polymer characterized by having a structural unit represented by the general formula (I):

wherein:

o, p is the number of repetitions of the repeating unit and is an integer greater than or equal to 1;

Ar¹and Ar²Each independently selected from an aromatic group having 5 to 50 ring atoms, a heteroaromatic group having 5 to 50 ring atoms or a non-aromatic group having 5 to 50 ring atoms, said aromatic, heteroaromatic and non-aromatic groups optionally being further substituted by one or more R¹Substituent group substitution;

T¹and T²Each independently an amide group; and when there are a plurality of T¹A plurality of said T¹Same or different, when there are a plurality of T²A plurality of said T²The same or different;

a, b are each independently 0 or 1, and at least one of a and b is 1;

R¹selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, substituted or unsubstituted silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, amido, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, C₃Cl, Br, F, crosslinkable groups, or withA substituted or unsubstituted aromatic or heteroaromatic group of 5 to 40 ring atoms, or a substituted or unsubstituted aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.
The polymer of claim 1, wherein T is¹And T²Selected from the structures shown in the general formula (II):

wherein R is³Has the same meaning as R¹The dotted lines indicate the linkages in the polymer.
The polymer of claim 2, wherein T is¹And T²Each independently containing one or more of the following structures:

n₁represents an integer of 0 to 30.
The polymer of any one of claims 1-3, wherein Ar is Ar¹Selected from the group comprising:

wherein, when there are plural X, plural of X are the same or different; x is CR⁴Or N;

when there are plural Y, plural of Y are the same or different; y is CR⁴R⁵、SiR⁴R⁵、NR⁴C (═ O), S, or O; r⁴、R⁵、R⁶The same meaning as that ofR¹。
The polymer of any one of claims 1 to 4, wherein at least one Ar in formula (I) is present²Containing a hole transport unit selected from the group consisting of: aromatic amines, triphenylamines, naphthylamines, thiophenes, carbazoles, dibenzothiophenes, dithienocyclopentadienes, dithienothioles, dibenzoselenophenes, furans, thiophenes, benzofurans, benzothiophenes, benzoselenophenes, carbazoles, and indocarbazoles and derivatives thereof.
The polymer of any one of claims 1-5, wherein there is at least one Ar²Selected from the group comprising one or more of the following structures:

wherein Ar is³-Ar¹¹Each occurrence is independently selected from a substituted or unsubstituted aromatic having 5 to 40 ring atoms, a substituted or unsubstituted heteroaromatic having 5 to 40 ring atoms, a substituted or unsubstituted aryloxy having 5 to 40 ring atoms, a substituted or unsubstituted heteroaryloxy having 5 to 40 ring atoms, or a substituted or unsubstituted non-aromatic having 5 to 40 ring atoms.
The polymer of any one of claims 1 to 5, wherein at least one Ar in formula (I) is present²Comprising an electron transport unit selected from the group consisting of: pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, benzisoxazole, bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenanthroline, quinoxaline, pyrazine, quinoline, and pharmaceutically acceptable salts thereof,Phenoxazines, benzofuropyridines, bipyridofurans, benzothienopyridines, bipyridylthiophenes, phenylselenopyridines and bipyridylselenophenes and derivatives thereof.
The polymer of claim 7, wherein the electron transport unit is a group having a backbone of any one of the following structural formulae:

wherein t represents an integer of 1 to 20; r⁷Independently at each occurrence, selected from hydrogen, deuterium, a halogen atom (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl;

X₁-X₈at each occurrence, is independently selected from CR⁸Or N, and at least one is N;

M¹、M²and M³Is at least one of absent, or M¹、M²Or M³When present, each is independently selected from: n (R)⁸)、C(R⁸)₂、Si(R⁸)₂、O、C＝N(R⁸)、C＝C(R⁸)₂、P(R⁸)、P(＝O)R⁸S, S ═ O or SO₂；

Ar¹²-Ar¹⁶Has the same meaning as Ar³；R⁸Has the same meaning as R¹。
The polymer of any one of claims 1 to 8, comprising at least one crosslinkable group; the crosslinkable group is selected from: linear alkenyl, cyclic alkenyl, linear dienyl, alkynyl, alkenyloxy, dienyloxy, acrylic, glycidyloxy, epoxybutynyl, silyl, cyclobutynyl.
The polymer according to any one of claims 1 to 8, comprising a structural unit represented by any one of the following general formulae (II-1) to (II-10):

wherein R is¹¹、R¹²And R¹³Is as defined for R³；

A is a substituted or unsubstituted aromatic group having 5 to 30 ring atoms, a substituted or unsubstituted aromatic group having 5 to 30 rings

A heteroaromatic group of atoms, or a substituted or unsubstituted non-aromatic group having 5 to 30 ring atoms; l is absent, or is CH₂(ii) a 0 < e <1, 0 < f <1, and e + f ═ 1.
The polymer according to any one of claims 1 to 10, comprising a structural unit represented by the general formula (III-1):

R¹⁴、R¹⁵each independently is H or C1-C10 alkyl; r¹¹Is H, C1-C20 alkyl or vinyl; when there are more than one R¹¹When a plurality of said R¹¹The same or different.
The polymer of claim 11, having a structure represented by general formula (III-2):

the R is¹⁶And R¹⁷Each independently selected from: r¹¹Is H, C1-C6 alkyl or vinyl, and the R is¹⁶And R¹⁷Are not identical.
The polymer of any one of claims 1-12, wherein | of said polymer is defined as

(HOMO-1) -HOMO ≧ 0.3eV, wherein HOMO represents the highest occupied orbital of the polymer, and HOMO-1 represents the second highest occupied orbital of the polymer.
A mixture comprising at least one polymer according to any of claims 1 to 13 and at least one further organic functional material selected from the group consisting of hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitting materials, host materials and organic dyes.
A composition comprising at least one polymer according to any one of claims 1 to 13 or a mixture according to claim 14, and at least one organic solvent.
An organic electronic device comprising at least one polymer according to any of claims 1 to 13 or a mixture according to claim 14.
The organic electronic device according to claim 16, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode.