WO2022078456A1 - High polymer, composition and organic photoelectric device containing same, and use thereof - Google Patents

Abstract

Provided are a high polymer, a mixture, a composition and an organic photoelectric device containing same, and the use thereof. The high polymer comprises a repeating structural unit E on a side chain, and the repeating structural unit contains B and/or N, and has a narrow luminescence spectrum, thereby facilitating the realization of a higher color purity. Provided is a high polymer suitable for a printing process, which in turn reduces the manufacturing cost of organic photoelectric devices, in particular OLEDs.

Description

A kind of high polymer, composition containing the same, organic optoelectronic device and application technical field

The present invention relates to the field of electroluminescent materials, in particular to a high polymer, a composition containing the same, an organic optoelectronic device, and the application of the high polymer in organic optoelectronic devices, especially in organic photoluminescence and electroluminescence device applications. The present invention also relates to an organic optoelectronic device comprising the polymer according to the present invention, and a method for its preparation.

Background technique

Because of the synthetic diversity of organic semiconductor materials, the possibility to realize large-area flexible devices, low fabrication costs, and high-performance optical and electrical properties, organic light-emitting diodes (OLEDs) are used in the realization of novel optoelectronic devices, such as, In flat panel display and lighting applications, there is great potential. In order to improve the luminous efficiency of organic light-emitting diodes, various systems based on fluorescent and phosphorescent luminescent materials have been developed. Organic light emitting diodes using phosphorescent materials have achieved relatively high performance, such as an internal luminescence quantum efficiency of almost 100%. But so far, the phosphorescent materials with practical use value are iridium and platinum complexes. The raw materials are rare and expensive, and the synthesis of complexes is very complicated, so the cost is quite high. In addition, although the complexes of iridium and platinum can achieve high luminous efficiency, the emitting spectral lines are wide, resulting in low color purity. In 2016, Hatakeyama et al. discovered a class of BN compounds (see Hatakeyama et al., Adv. Mater. 2016, DOI: 10.1002/adma. 201505491), which have high luminous efficiency and narrow FWHM.

In order to take full advantage of the advantages of organic materials, it is hoped that OLEDs can be fabricated in a large area at low cost through a printing method. The existing reported BN compounds and their analogs have relatively low molecular weights, and their structural rigidity is not suitable for printing processes.

Therefore, new material systems suitable for printing need to be developed.

SUMMARY OF THE INVENTION

In view of the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a high polymer, a composition containing the same, an organic optoelectronic device and application, and to provide a new high polymer material to solve the problem that the existing materials are not suitable for on the printing process.

The technical scheme of the present invention is as follows:

A high polymer comprising repeating units as shown in chemical formula I:

wherein n is greater than or equal to 1, X is selected from O, S, CR ¹ R ² , SiR ¹ R ² , NR ³ , and the repeating unit E is selected from the structural units of the following chemical formula (1) or (2):

The symbols and signs used therein have the following meanings:

The same or different Ar ¹ to Ar ³ are selected from aromatic or heteroaromatic having 5-24 ring atoms;

The same or different Ar ⁴ to Ar ⁵ are selected from empty or aromatic or heteroaromatic with 5-24 ring atoms;

When Ar ⁴ to Ar ⁵ are not empty, X _a , X _b are selected from N, C(R ⁹ ), Si(R ⁹ ); Y _a , Y _b are selected from B, P=O, C(R ⁹ ) , Si(R ⁹ );

When Ar ⁴ to Ar ⁵ are empty, the corresponding X _a or Y _b is selected from N(R ⁹ ), C(R ⁹ R ¹⁰ ), Si(R ⁹ R ¹⁰ ), C=O, O, C=N (R ⁹ ), C=C(R ⁹ R ¹⁰ ), P(R ⁹ ), P(=O)R ⁹ , S, S=O or SO ₂ ;

X1 and X2 are empty or a bridging group;

R ¹ to R ¹⁰ may be the same or different selected substituents independently selected from H, D, -F, -Cl, Br, I, -CN, -NO ₂ , -CF ₃ , and have 1 to 20 C atoms straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy groups, or branched or cyclic alkyl, haloalkyl, alkoxy, thioalkane groups having 3 to 20 C atoms Oxy groups are either silyl groups, or substituted keto groups having 1 to 20 C atoms, or alkoxycarbonyl groups having 2 to 20 C atoms, or 7 to 20 Aryloxycarbonyl group of C atom, cyano group (-CN), carbamoyl group (-C(=O) _NH2 ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, Nitro groups, _CF3 groups, Cl, Br, F, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or 5 to 40 An aryloxy or heteroaryloxy group of 1 ring atoms, or an arylamino or heteroarylamino group with 5 to 40 ring atoms, a disubstituted unit in any position of the above substituents, or a combination of these systems, wherein one or more of the substituent groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded;

A mixture comprising a polymer as described above, and at least one other organic functional material.

A composition comprising a polymer as described above, and at least one organic solvent and/or one organic resin.

An organic optoelectronic device comprising a high polymer as described above.

Beneficial effects: the high polymer of the present invention has good solubility in organic solvents, good film-forming performance, and at the same time keeps the narrow emission line of the monomer, thereby providing a better material solution for printing OLED.

Detailed ways

The present invention provides a high polymer and its application in an organic electroluminescent device, an organic optoelectronic device comprising the high polymer and a preparation method thereof, in order to make the purpose, technical scheme and effect of the present invention clearer, It is clear that the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

The present invention provides a kind of high polymer, including repeating unit as shown in chemical formula I:

wherein n is greater than or equal to 1, X is selected from O, S, CR ¹ R ² , SiR ¹ R ² , NR ³ , and the repeating unit E is selected from the structural units of the following chemical formula (1) or (2):

The symbols and signs used therein have the following meanings:

The same or different Ar ¹ to Ar ³ are selected from aromatic or heteroaromatic having 5-24 ring atoms;

The same or different Ar ⁴ to Ar ⁵ are selected from empty or aromatic or heteroaromatic with 5-24 ring atoms;

When Ar ⁴ to Ar ⁵ are not empty, X _a , X _b are selected from N, C(R ⁹ ), Si(R ⁹ ); Y _a , Y _b are selected from B, P=O, C(R ⁹ ) , Si(R ⁹ );

When Ar ⁴ to Ar ⁵ are empty, the corresponding X _a or Y _b is selected from N(R ⁹ ), C(R ⁹ R ¹⁰ ), Si(R ⁹ R ¹⁰ ), C=O, O, C=N (R ⁹ ), C=C(R ⁹ R ¹⁰ ), P(R ⁹ ), P(=O)R ⁹ , S, S=O or SO ₂ ;

X ¹ , X ² are empty or a bridging group;

R ¹ to R ¹⁰ may be the same or different selected substituents independently selected from H, D, -F, -Cl, Br, I, -CN, -NO ₂ , -CF ₃ , and have 1 to 20 C atoms straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy groups, or branched or cyclic alkyl, haloalkyl, alkoxy, thioalkane groups having 3 to 20 C atoms Oxy groups are either silyl groups, or substituted keto groups having 1 to 20 C atoms, or alkoxycarbonyl groups having 2 to 20 C atoms, or 7 to 20 Aryloxycarbonyl group of C atom, cyano group (-CN), carbamoyl group (-C(=O) _NH2 ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, Nitro groups, _CF3 groups, Cl, Br, F, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or 5 to 40 An aryloxy or heteroaryloxy group of 1 ring atoms, or an arylamino or heteroarylamino group with 5 to 40 ring atoms, a disubstituted unit in any position of the above substituents, or a combination of these systems, One or more of the substituent groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the group is bonded.

In a preferred embodiment, X is selected from CR ¹ R ² ; particularly preferably, X is selected from CH ₂ .

In some preferred embodiments, at least one of the bridging groups X ¹ and X ² is empty; it is particularly preferred that both are empty, and the repeating structural unit E is selected from the group consisting of the following chemical formula (1b) or (2b) or the structural unit shown:

In some preferred embodiments, at least one of X ¹ and X ² is a single bond; it is particularly preferred that both are single bonds, and the repeating structural unit E is selected from the group consisting of the following chemical formula (1c) or ( 2c) The structural unit shown:

In certain embodiments, when X ¹ and X ² appear, the same or different are two-bridged groups, and the preferred two-bridged groups are:

wherein the symbols R ₃ , R ₄ and R ₅ are defined as R ¹ as described above, and the dashed bond shown in the above group represents a bond bonded to an adjacent structural unit.

For the purposes of the present invention, an aromatic ring system includes in the ring system

carbon atoms, the heteroaromatic ring system contains in the ring system

carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 4. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only systems of aryl or heteroaryl groups, but also systems in which multiple aryl or heteroaryl groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diarylether, etc., are also considered to be aromatic ring systems for the purpose of this invention.

For the purpose of the present invention, wherein the H atom on NH or the bridging group CH ₂ group can be substituted by R ¹ group; preferably, R ¹ can be selected from, (1) C1-C10 alkyl, particularly preferably refers to The following groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoro Ethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, acetylene radical, propynyl, butynyl, pentynyl, hexynyl and octynyl; (2)

Alkoxy, particularly preferred is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methyl Butoxy; (3) C2 to C10 aryl or heteroaryl, which can be monovalent or divalent depending on the application, also substituted in each case by the above-mentioned radicals R ¹ and can be passed through Any desired position is attached to an aromatic or heteroaromatic ring, particularly preferred refers to the following groups: benzene, naphthalene, anthracene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, butane, pentane, Benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiofluorene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline , isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyridine azole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthroimidazole, pyridimidazole, pyrazinimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthraxazole azole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazepine Anthracene, 1,5-naphthalene, nitrogen carbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2 ,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2 ,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3 - Triazine, tetrazole. 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are taken to mean, in particular, biphenylene, terphenylene, fluorene, spirobifluorene, dihydrogen, in addition to the aryl and heteroaryl groups mentioned above. phenanthrene, tetrahydropyrene and cis- or trans-indenofluorene.

In a preferred embodiment, it comprises a compound of formula (1)-(1e) or (2)-(2e), wherein Ar ¹ to Ar ⁵ which are the same or different in each occurrence can be selected from having 5 to 20 Aromatic and heteroaromatic having 1 ring atoms; preferably selected from aromatic and heteroaromatic having 5 to 18 ring atoms; more preferably selected from aromatic and heteroaromatic having 5 to 15 ring atoms; most preferred is selected from aromatic and heteroaromatic having 5 to 10 ring atoms; they may be unsubstituted or substituted with one or two R ¹ groups. Preferred aryl or heteroaryl groups are benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene or thiophene.

In another preferred embodiment, Ar ¹ to Ar ⁵ comprise the following structural formulae, each of which may be substituted with one or more groups R ¹ .

X ₃ is CR ⁶ or N;

Y ₇ is selected from CR ⁷ R ⁸ , SiR ⁹ R ¹⁰ , NR ⁶ or, C(=O), S, or O; R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are as defined above.

Further, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ can be independently selected from one of the following chemical structural formulas or a combination thereof, which can be further optionally substituted:

For the purpose of the present invention, according to the structural units of formula (1)-(1e) or (2)-(2e), in a particularly preferred embodiment, Ar ¹ to Ar ⁵ are phenyl groups.

In a particularly preferred embodiment, according to the polymer of the present invention, the repeating structural unit E comprises a structural unit represented by the following chemical formula (1a) or (2a):

Among them, X ¹ and X ² are preferably selected from O, S, particularly preferably from O.

In another particularly preferred embodiment, according to the polymer of the present invention, the repeating structural unit E comprises a structural unit represented by the following chemical formula (1d) or (2d) or (1e) or (2e):

Preferably, Y _b in formulas (2d) and (2e) are the same or different and are independently selected from C=O, O, P(=O)R ⁹ , S=O or SO ₂ ; particularly preferably selected from C=O.

Preferably, X _a in formulas (1d) and (1e) are the same or different and are independently selected from N(R ⁹ ), C(R ⁹ R ¹⁰ ), Si(R ⁹ R ¹⁰ ), O, S.

In some preferred embodiments, in the structural units according to the Institute of Chemistry (1), (2), (1a)-(1e), (2a)-(2e), wherein R ⁴ to R ⁸ appear multiple times can contain the following structural units or their combinations identically or differently:

where n is 1 or 2 or 3 or 4.

In the embodiments of the present invention, for the energy level structure of organic materials, triplet energy level (T1) and singlet energy level (S1), HOMO, LUMO, play a key role. The determination of these energy levels is described below.

HOMO and LUMO energy levels can be measured by the photoelectric effect, such as XPS (X-ray Photoelectron Spectroscopy) and UPS (Ultraviolet Photoelectron Spectroscopy) or by Cyclic Voltammetry (hereafter CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet energy level T1 of organic materials can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.), the specific simulation method can be obtained. See WO2011141110.

The singlet energy level S1 of organic materials can be determined by absorption spectroscopy or emission spectroscopy, or obtained by quantum simulation calculations (such as Time-dependent DFT).

It should be noted that the absolute values of HOMO, LUMO, T1 and S1 depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as onset and peak point on the CV curve, can give different HOMO /LUMO value. Therefore, reasonably meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiment of the present invention, the values of HOMO, LUMO, T1 and S1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

The advantage of the polymer according to the present invention is that the repeating units E are connected through the non-conjugated polymer main chain to achieve a higher molecular weight, while maintaining the energy structure of a single repeating unit, that is, the HOMO of a single repeating unit, LUMO, S1 and T1 remain largely unchanged.

In certain preferred embodiments, Δ(S1(E)-T1(E)) ≤ 0.30 eV, preferably ≤ 0.25 eV, more preferably ≤ 0.20 eV, more preferably ≤ 0.15 eV, most preferably ≤0.10eV.

According to the polymer of the present invention, E is an emitter. Generally speaking, the specific gravity of the light-emitting body in the light-emitting layer has a certain range. In certain embodiments, the content of the repeating unit E in the polymer is from 0.1 mol%≤90 mol%.

In a preferred embodiment, the content of repeating units E in the polymer is from 1 mol% to 80 mol%, preferably from 2 mol% to 70 mol%, more preferably from 3 mol% to 50 mol%, most preferably from 3 mol% to 30 mol%.

In this embodiment of the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and can be interchanged.

In the embodiments of the present invention, singlet state and singlet state have the same meaning and can be interchanged.

In this embodiment of the present invention, triplet state and triplet state have the same meaning and can be interchanged.

The term "small molecule" as defined herein refers to molecules that are not polymers, oligomers, dendrimers, or blends. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤3000 g/mol, preferably ≤2000 g/mol, most preferably ≤1500 g/mol.

High polymer, namely Polymer, includes homopolymer (homopolymer), copolymer (copolymer), mosaic copolymer (block copolymer). In addition, in the present invention, high polymers also include dendrimers. For the synthesis and application of dendrimers, please refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

Conjugated polymer (conjugated polymer) is a high polymer, its main chain backbone is mainly composed of sp2 hybrid orbital of C atom, famous examples are: polyacetylene and poly(phenylene vinylene), its main chain The C atoms on the main chain can also be replaced by other non-C atoms, and when the sp2 hybridization on the main chain is interrupted by some natural defects, it is still considered as a conjugated polymer. In addition, the conjugated polymer in the present invention also includes arylamine, aryl phosphine and other heteroaromatics (heteroarmotics), organometallic complexes on the main chain. )Wait.

In the present invention, the repeating structural unit E, in the case of multiple occurrences, can be independently selected from the same or different structural groups.

In some preferred embodiments, the high polymer has a half maximum width (FWHM) of photoluminescence spectral lines ≤ 55 nm, preferably ≤ 45 nm, more preferably ≤ 40 nm, especially ≤ 35 nm, most Preferably ≤30nm.

Examples of suitable repeating structural units according to the invention are given below, which may be optionally further optionally substituted:

In a preferred embodiment, the polymer according to the present invention further contains another organic functional group.

In certain embodiments, polymers according to the present invention have the following general formula:

The definition of Y is the same as the definition of X, F is the other organic functional group, and n and m are integers greater than or equal to 1.

The other organic functional group F, when present in multiples, can be independently selected from the same or different groups for hole (also called hole) injection or transport, hole blocking group, electron injection Or transport groups, electron blocking groups, organic host groups, singlet light-emitting groups (fluorescent light-emitting groups), triplet light-emitting groups (phosphorescence light-emitting groups). These organic functional groups all correspond to the corresponding small molecule organic functional materials: hole (also called hole) injection or transport material (HIM/HTM), hole blocking material (HBM), electron injection or transport material (EIM/HTM) ETM), electron blocking material (EBM), organic host material (Host), singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally excited delayed fluorescent material (TADF). These organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of these three patent documents are hereby incorporated by reference.

In a preferred embodiment, the polymer according to the present invention comprises the aforementioned E, and another organic functional group F, wherein F is selected from triplet matrix groups.

In another preferred embodiment, the polymer according to the present invention comprises the aforementioned E, and another organic functional group F, wherein F is selected from triplet light-emitting groups.

In another preferred embodiment, the polymer according to the present invention comprises the aforementioned E, and another organic functional group F, wherein F is selected from TADF light-emitting groups.

In another preferred embodiment, the polymer according to the present invention comprises the aforementioned E, and two other organic functional groups F1 and F2, wherein F1 is selected from the triplet matrix group, and F2 is selected from the triplet state luminescent group.

In another preferred embodiment, the polymer according to the present invention contains the aforementioned E, and two other organic functional groups F1 and F2, wherein F1 is selected from hole transport groups and F2 is selected from electron transport groups group.

In a more preferred embodiment, the polymer according to the present invention comprises the aforementioned E, and another organic functional group F, wherein F is selected from singlet matrix groups.

In another more preferred embodiment, the polymer according to the present invention comprises the aforementioned E, and two other organic functional groups F1 and F2, wherein F1 is selected from singlet matrix groups, and F2 is selected from Self-singlet emitting group.

The singlet matrix groups and triplet matrix groups are described in more detail below (but not limited thereto).

1. Triplet Host:

Examples of triplet host materials are not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy level is higher than that of an emitter, especially a triplet emitter or a phosphorescent emitter .

Examples of metal complexes that can be used as triplet hosts include, but are not limited to, the following general structures:

M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ⁴ are independently selected from C, N, O, P, and S; L is an auxiliary ligand; m is an integer , which has a value from 1 to the maximum coordination number of the metal; in a preferred embodiment, metal complexes that can be used as triplet hosts are of the form:

(O-N) is a bidentate ligand in which the metal is coordinated to O and N atoms. m is an integer ranging from 1 to the maximum coordination number of this metal;

In a certain embodiment, M can be selected from Ir and Pt.

Examples of organic compounds that can serve as triplet hosts are selected from compounds containing cyclic aromatic hydrocarbon groups, such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolecarbazole, pyridine indole, pyrrole dipyridine, Pyrazoles, imidazoles, triazoles, oxazoles, thiazoles, oxadiazoles, oxtriazoles, dioxazoles, thiadiazoles, pyridines, pyridazine, pyrimidines, pyrazines, triazines, oxazines, oxthiazines , oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthalene, quinazoline, Quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furanopyridine, benzothiophenepyridine, thiophenepyridine, benzoselenophene Pyridines and selenophene benzodipyridines; groups containing 2 to 10 ring structures, which may be of the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, directly with each other or through at least one of the following groups Linked together, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and alicyclic groups. Wherein, each Ar can be further substituted, and the substituents can be selected from hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl base.

In a preferred embodiment, the triplet host material can be selected from compounds comprising at least one of the following groups:

Wherein: when Y appears multiple times, Y is independently selected from C(R) ₂ or NR or O or S; when X appears multiple times, X is independently selected from CR or N, and Ar ¹ to Ar ³ For aryl or heteroaryl, R can be selected from the following groups: hydrogen, deuterium, halogen (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl , aralkyl, heteroalkyl, aryl and heteroaryl, and n is selected from an integer from 1 to 20.

Examples of suitable triplet host materials are listed in the table below but are not limited to:

2. Singlet Host:

Examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of an emitter, particularly a singlet emitter or a fluorescent emitter.

Examples of the organic compound used as the singlet host material can be selected from the group consisting of ring-containing aromatic hydrocarbon compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, chrysene, perylene, Azulene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolecarbazole, pyridine Indole, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine , oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indole, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, Quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenepyridine, thiophenedipyridine , benzoselenophenepyridines and selenophenedipyridines; groups containing 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, directly connected to each other or through at least one of the following The groups are linked together, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and alicyclic groups.

In a preferred embodiment, the singlet host material can be selected from compounds comprising at least one of the following groups:

Each occurrence of Y is independently selected from C(R) ² or NR or O or S, each occurrence of X is independently selected from CR or N, and each occurrence of R is independently selected from the following groups: hydrogen, Deuterium, halogen atoms (F,Cl,Br,I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, n is selected from Integer from 1 to 20.

In some preferred embodiments, the singlet state body is selected from anthracene derivatives, such as CN102224614 B, CN 100471827C, CN 1914293B, WO2015033559A1, US2014246657A1, WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, CN102428158B the like as disclosed in Patent Document.

The following table lists some examples of anthracene-based singlet host materials:

In some more preferred embodiments, the anthracene-based singlet host material is deuterated, that is, the host material molecule contains at least one deuterium atom. Such examples are described in patent documents such as CN102369256B, CN102428158B, CN102639671B, US2015021586A1, etc. public.

The present invention also provides a polymerizable monomer having the following general formula:

Wherein, the structural unit E includes a structure as shown in any one of chemical formulae (1)-(1e) or (2)-(2e).

In a preferred embodiment, the polymerizable monomer is characterized in that (S1(E)-T1(E))≤0.30eV, preferably ≤0.25eV, more preferably ≤0.20eV, Preferably ≤0.10eV.

The present invention also provides a mixture comprising at least one polymer as described above and another organic functional material, the organic functional material can be selected from a hole (also called hole) injection or transport material (HIM) /HTM), hole blocking material (HBM), electron injection or transport material (EIM/ETM), electron blocking material (EBM), organic host material (Host), singlet emitter (fluorescent emitter), triplet Emitters (phosphorescent emitters), and Thermally Excited Delayed Fluorescent Materials (TADFs). These functional materials have been described above.

The present invention also relates to a composition comprising a polymer or polymerizable monomer as described above and at least one organic solvent and/or an organic resin.

In a preferred embodiment, the composition comprises an organic solvent. Examples of organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, 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, naphthalene alkanes, indene and/or mixtures thereof.

In a preferred embodiment, the composition according to the present invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The composition in the embodiment of the present invention may include 0.01 to 20 wt % of the high polymer, preferably 0.1 to 15 wt %, more preferably 0.2 to 10 wt %, and most preferably 0.25 to 5 wt % of the high polymer .

In a preferred embodiment, the composition comprises an organic resin. In another preferred embodiment, the composition comprises two or more organic resins. For the purpose of the present invention, the organic resin refers to a resin prepolymer or a resin formed after crosslinking or curing thereof.

Organic resins suitable for the present invention include but are not limited to: polystyrene, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polybutene, Polyethylene glycol, polysiloxane, polyacrylate, epoxy resin, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride (PVDC), polystyrene-acrylonitrile (SAN), polyterephthalic acid Butylene Glycol (PBT), Polyethylene Terephthalate (PET), Polyvinyl Butyrate (PVB), Polyvinyl Chloride (PVC), Polyamide, Polyoxymethylene, Polyimide, Polyether imide or mixtures thereof.

Further, organic resins suitable for the present invention include, but are not limited to, the following monomers (resin prepolymers) formed by homopolymerization or copolymerization: styrene derivatives, acrylate derivatives, acrylonitrile derivatives, acrylamide derivatives, Vinyl ester derivatives, vinyl ether derivatives, maleimide derivatives, conjugated diene derivatives.

Examples of styrene derivatives are: alkylstyrenes such as α-methylstyrene, o-, m-, p-methylstyrene, p-butylstyrene, especially p-tert-butylstyrene, alkane Oxystyrene such as p-methoxystyrene, p-butoxystyrene, p-tert-butoxystyrene.

Examples of acrylate derivatives are: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate ester, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate -Hydroxybutyl, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate , allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, methyl methacrylate 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiglycol acrylate, methoxydiglycol methacrylate, Methoxytriethylene glycol acrylate, Methoxytriethylene glycol methacrylate, Methoxypropanediol acrylate, Methoxypropanediol methacrylate, Methoxydipropyleneglycol acrylate, Methoxydipropyleneglycol methacrylate base acrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-Hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; 2-aminoethyl acrylate, methacrylic acid 2-aminoethyl ester, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl (meth)acrylic acid, N,N-diethyl Aminoethyl (meth)acrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, acrylic acid 3-Aminopropyl, 3-aminopropyl methacrylate, benzyl N,N-dimethyl-1,3-propanediamine(meth)acrylate, 3-dimethylaminopropyl acrylate and methyl methacrylate 3-dimethylaminopropyl acrylate; glycidyl acrylate and glycidyl methacrylate;

Examples of acrylonitrile derivatives are: acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile and vinylidene cyano;

Examples of acrylamide derivatives are: acrylamide, methacrylamide, alpha-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide;

Examples of vinyl ester derivatives are: vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Examples of vinyl ether derivatives are: vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Examples of maleimide derivatives are: maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide;

Examples of conjugated diene derivatives are: 1,3-butadiene, isoprene and chloroprene;

Said homopolymers or copolymers can be prepared, for example, by free radical polymerization, cationic polymerization, anionic polymerization or organometallic catalyzed polymerization (eg Ziegler-Natta catalysis). The polymerization process can be suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization.

Said organic resin generally has an average molar mass Mn (determined by GPC) of 10 000-1 000 000 g/mol, preferably 20 000-750 000 g/mol, more preferably 30 000-500 000 g/mol.

In some preferred embodiments, the organic resin is a thermosetting resin or an ultraviolet (UV) curable resin. In some embodiments, the organic resin is cured in a method that will facilitate roll-to-roll processing.

Thermoset resins require curing, during which they undergo an irreversible molecular cross-linking process, which makes the resin non-meltable. In some embodiments, the thermosetting resin is epoxy resin, phenolic resin, vinyl resin, melamine resin, urea-formaldehyde resin, unsaturated polyester resin, polyurethane resin, allyl resin, acrylic resin, polyamide resin, polyamide - imide resins, phenolamine polycondensation resins, urea melamine polycondensation resins or combinations thereof.

In some embodiments, the thermoset resin is an epoxy resin. Epoxies cure easily and do not emit volatiles or by-products from a wide range of chemicals. Epoxies are also compatible with most substrates and tend to wet surfaces easily. See Boyle, M.A. et al., "Epoxy Resins", Composites, Vol. 21, ASM Handbook, pages 78-89 (2001).

In some embodiments, the organic resin is a silicone thermoset resin. In some embodiments, the silicone thermoset resin is OE6630A or OE6630B (Dow Corning Corporation (Auburn, MI)).

In some embodiments, thermal initiators are used. In some embodiments, the thermal initiator is AIBN [2,2'-azobis(2-methylpropionitrile)] or benzoyl peroxide.

UV curable resins are polymers that will cure and harden rapidly when exposed to specific wavelengths of light. In some embodiments, the UV curable resin is a resin having free radical polymerizable groups as functional groups, cationically polymerizable groups such as (meth)acryloyloxy groups, vinyl groups an oxy group, a styryl group or a vinyl group; the cationically polymerizable group is, for example, an epoxy group, a thioepoxy group, a vinyloxy group or an oxetane alkyl group. In some embodiments, the UV curable resin is polyester resin, polyether resin, (meth)acrylic resin, epoxy resin, polyurethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, or sulfur Alkene resin.

In some embodiments, the UV curable resin is selected from the group consisting of urethane acrylates, allyloxylated cyclohexyl diacrylate, bis(acryloyloxyethyl)hydroxyisocyanurate, bis(acryloyloxy) Neopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate , 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, dicyclopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate , dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, bis(trimethylolpropane) tetraacrylate, triethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol Diacrylate, Neopentyl Glycol Dimethacrylate, Neopentyl Glycol Hydroxypivalate Diacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Phosphate Dimethacrylate, Polyethylene Glycol Diacrylate , polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglyceride diacrylate, trimethylolpropane triacrylate, tripropylene glycol Diacrylate, Tris(acryloyloxyethyl)isocyanurate, Phosphate Triacrylate, Phosphate Diacrylate, Phenyl Acrylate, Vinyl Terminated Polydimethylsiloxane, Vinyl Block Terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated difluoromethylsiloxane-dimethylsiloxane copolymer , Vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane, monomethacryloyloxypropyl-terminated polydimethylsiloxane, monoethylene Group terminated polydimethylsiloxane, monoallyl-monotrimethylsiloxy terminated polyethylene oxide, and combinations thereof.

In some embodiments, the UV curable resin is a thiol functional compound that can be crosslinked with isocyanates, epoxy resins, or unsaturated compounds under UV curing conditions. In some embodiments, the thiol-functional compound is a polythiol. In some embodiments, the polythiol is pentaerythritol tetrakis(3-mercaptopropionate) (PETMP); trimethylolpropane tris(3-mercaptopropionate) (TMPMP); ethylene glycol bis(3-mercaptopropionate) propionate) (GDMP); tris[25-(3-mercapto-propionyloxy)ethyl]isocyanurate (TEMPIC); dipentaerythritol hexa(3-mercaptopropionate) (Di-PETMP) ; Ethoxylated trimethylolpropane tris(3-mercaptopropionate) (ETTMP 1300 and ETTMP 700); Polycaprolactone tetrakis(3-mercaptopropionate) (PCL4MP1350); Pentaerythritol tetramercaptoacetate (PETMA); Trimethylolpropane Trimercaptoacetate (TMPMA); or Ethylene Glycol Dimercaptoacetate (GDMA). These compounds are sold by Bruno Bock (Marschacht, Germany) under the trade name

sell.

In some embodiments, the UV curable resin further includes a photoinitiator. The photoinitiator will initiate a crosslinking and/or curing reaction of the photosensitive material during exposure to light. In some embodiments, the photoinitiator is acetophenone-based, benzoin-based, or thioxanthone-based.

In some embodiments, the UV curable resin comprises a thiol functional compound and a methacrylate, acrylate, isocyanate, or combination thereof. In some embodiments, the UV curable resin includes a polythiol and a methacrylate, acrylate, isocyanate, or combination thereof.

In some embodiments, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd (Korea)).

In some embodiments, the photoinitiator is

127.

184.

184D,

2022,

2100,

250,

270,

2959,

369.

369EG,

379、

500,

651.

754.

784、

819.

819DW,

907.

907FF,

OxeOl,

TPO-L,

1173,

1173D,

4265,

BP or

MBF (BASF Corporation (Wyandotte, Michigan)). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenyl-oxyphenone) or MBF (methyl benzoylformate).

In some embodiments, the organic resin is from about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 50% to about 95% by weight of the composition (w/w) 85%, about 50% to about 80%, about 50% to about 70%, about 50% to about 60%, about 60% to about 99%, about 60% to about 95%, about 60% to about 90% , about 60% to about 85%, about 60% to about 80%, about 60% to about 70%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 85%, about 70% to about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, about 80% to about 85%, about 85% to about 99%, about 85% to about 95%, about 85% to about 90%, about 90% to about 99%, about 90% to about 95%, or between about 95% to about 99%.

The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic optoelectronic devices, particularly preferred is a preparation method by printing or coating.

Among them, suitable printing or coating techniques include, but are not limited to, ink jet printing, typography, screen printing, dip coating, spin coating, knife coating, roll printing, twist roll printing, lithography, flexo printing Printing, rotary printing, spraying, brushing or pad printing, slit extrusion coating, etc. Preferred are gravure printing, screen printing and inkjet printing. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders, etc., to adjust viscosity, film-forming properties, improve adhesion, and the like. For detailed information on printing technology and its related requirements for the solution, such as solvent and concentration, viscosity, etc., please refer to the "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan (Handbook of Print Media: Technologies and Production Methods) ), ISBN 3-540-67326-1.

Based on the above-mentioned high polymer, the present invention also provides an application of the above-mentioned high polymer, that is, applying the high polymer to an organic optoelectronic device, and the organic optoelectronic device can be selected from, but not limited to, organic light-emitting Diodes (OLED), Organic Photovoltaics (OPV), Organic Light Emitting Cells (OLEEC), Organic Field Effect Transistors (OFET), Organic Light Emitting Field Effect Transistors, Organic Lasers, Organic Spin Optoelectronic Devices, Organic Sensors and Organic Plasmons Emitting diode (Organic Plasmon Emitting Diode), etc., especially OLED. In the embodiment of the present invention, the organic compound is preferably used in the light-emitting layer of the OLED device.

In a preferred embodiment, the polymer is used in the light-emitting layer of an OLED device.

The present invention further relates to an organic optoelectronic device comprising at least one polymer as described above. Generally, such an organic optoelectronic device comprises at least a cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer contains at least one of the above-mentioned polymers. The organic optoelectronic device can be selected from, but not limited to, organic light emitting diodes (OLED), organic photovoltaic cells (OPV), organic light emitting cells (OLEEC), organic field effect transistors (OFET), organic light emitting field effect transistors, organic Lasers, organic spin optoelectronic devices, organic sensors and organic plasmon emission diodes (Organic Plasmon Emitting Diode), and color conversion devices.

The color converting device may be a down-converting color converter for making color displays in which blue light is converted into green and red light.

In a particularly preferred embodiment, the organic optoelectronic device is an OLED, which includes a substrate, an anode, at least one light-emitting layer, and a cathode.

The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting device. See, eg, Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably the substrate has a smooth surface. Substrates free of surface defects are particularly desirable. In a preferred embodiment, the substrate is flexible, optionally a polymer film or plastic, with a glass transition temperature Tg above 150°C, preferably above 200°C, more preferably above 250°C, most preferably over 300°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 the hole injection layer (HIL) or hole transport layer (HTL) or light emitting 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 as a HIL or HTL or electron blocking layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. 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 those 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 fabricate devices according to the present invention.

The cathode may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the emissive layer. In one embodiment, the work function of the cathode and the LUMO level of the emitter in the emissive layer or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, more preferably less than 0.2 eV. In principle, all materials that can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloys, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can 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.

OLEDs can also contain other functional layers such as hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), electron injection layer (EIL), electron transport layer (ETL), hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents are hereby incorporated by reference.

In a preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer thereof is prepared by printing the composition of the present invention.

According to the light-emitting device of the present invention, the light-emitting wavelength is between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

The present invention also relates to the use of organic optoelectronic devices according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

The present invention also relates to electronic devices incorporating organic optoelectronic devices according to the present invention, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

The present invention will be described below with reference to the preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should It is recognized that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

specific embodiment

1. Monomer synthesis

(1) Synthesis of monomer E1

The synthetic route is shown in the figure below:

The synthesis steps are as follows:

a. Under nitrogen environmental protection, 10 mmol of compound 1 was dissolved in 250 ml of dry DMF solution, the resulting reaction solution was placed in an ice bath and stirred, and 11.0 mmol of phosphorus oxychloride (POCl ₃ ) solution was added dropwise, and the dropwise addition was completed. Then, continue the reaction for 30 minutes, gradually warm to room temperature and react for 2 hours, add water to quench the reaction, extract with dichloromethane, wash with water, combine the organic phases, dry with anhydrous sodium sulfate, filter, and evaporate the organic solvent to dryness to obtain compound 2 The crude product was recrystallized with dichloromethane and n-hexane to obtain a product of 7.5 mmol, yield: 75.0%. Vacuum dry for use. MS(ASAP)=448.2.

b. 5.0 mmol of compound 2 obtained above was dissolved in 200 ml of dry tetrahydrofuran (THF) solution, under nitrogen environmental protection, the reaction solution was stirred at a temperature of -78° C., and 8.0 mmol of methylene triphenylphosphine was added dropwise. (Wittig reagent), after the addition is completed, gradually rise to room temperature, continue to stir at room temperature overnight, add water to quench the reaction, all reaction solutions are extracted with dichloromethane, the organic phase is washed with water, and finally the organic phases are combined, and anhydrous sulfuric acid is used. Dry with sodium, filter, evaporate the organic solvent to dryness, and purify the obtained product with a silica gel column. The mobile phase is chloroform:petroleum ether=1:2, finally obtaining 3.85mmol of monomer E1, yield: 77.0%. Dry under vacuum for use. MS(ASAP)=446.2.

(2) Synthesis of monomer E2

The synthetic route is shown in the figure below:

The synthesis steps are as follows:

a. The synthesis method is similar to that of monomer E1, yield: 74.8%. Vacuum dry for use. MS(ASAP)=728.4.

b. The synthesis method is similar to the synthesis method of monomer E1, and the yield: 78.9%. Dry under vacuum for use. MS(ASAP)=726.4.

(3) Synthesis of monomer E3:

The synthetic route is shown in the figure below:

The synthesis steps are as follows:

a. The synthesis method is similar to that of monomer E1, yield: 76.7%. Vacuum dry for use. MS(ASAP)=417.1.

b. The synthesis method is similar to that of monomer E1, yield: 79.5%. Dry under vacuum for use. MS(ASAP)=417.1.

(4) Synthesis of monomer E4:

The synthetic route is shown in the figure below:

The synthesis steps are as follows:

a. Under nitrogen environmental protection, 10 mmol of compound 1 was dissolved in 250 ml of dry THF solution, the resulting reaction solution was placed in an ice bath and stirred, and 11.0 mmol of n-BuLi (n-BuLi) solution was added dropwise. After the completion, the reaction was continued for 30 minutes, and 11.0 mmol of DMF solvent was added dropwise. After the dropwise addition, the reaction was gradually raised to room temperature and reacted for 2 hours. The reaction was quenched by adding water, extracted with dichloromethane, washed with water, and the organic phases were combined. Dry over sodium sulfate, filter, and evaporate the organic solvent to dryness to obtain the crude product of compound 2. The crude product is recrystallized from dichloromethane and n-hexane to obtain a product of 7.55 mmol, yield: 75.5%. Vacuum dry for use. MS(ASAP)=545.2.

b. The synthesis method is similar to that of monomer E1, yield: 88.4%. Dry under vacuum for use. MS(ASAP)=543.2.

(5) Synthesis of monomer E5:

The synthesis steps are as follows:

a. The synthesis method is similar to that of monomer E4, yield: 74.7%. Vacuum dry for use. MS(ASAP)=723.3.

b. The synthesis method is similar to that of monomer E1, yield: 81.4%. Dry under vacuum for use. MS(ASAP)=721.3.

(5) Synthesis of monomer F1

The synthetic experimental route is shown in the figure below:

The synthesis steps are as follows:

a. Under nitrogen environmental protection, 10 mmol of compound 1 was dissolved in 250 ml of dry THF solution, the resulting reaction solution was placed in an ice bath and stirred, and 11.0 mmol of n-BuLi (n-BuLi) solution was added dropwise. After the completion, the reaction was continued for 30 minutes, and 11.0 mmol of DMF solvent was added dropwise. After the dropwise addition, the reaction was gradually raised to room temperature and reacted for 2 hours. The reaction was quenched by adding water, extracted with dichloromethane, washed with water, and the organic phases were combined. Dry with sodium sulfate, filter, and evaporate the organic solvent to dryness to obtain the crude product of compound 2. The crude product is recrystallized from dichloromethane and n-hexane to obtain a product of 7.8 mmol, yield: 78.0%. Vacuum dry for use. MS(ASAP)=685.2.

b. 5.0 mmol of compound 2 obtained above was dissolved in 200 ml of dry tetrahydrofuran (THF) solution, and under nitrogen environmental protection, the reaction solution was stirred at a temperature of -78° C., and 8.0 mmol of methylene triphenylphosphine was added dropwise. (Wittig reagent), after the addition is completed, gradually rise to room temperature, continue to stir at room temperature overnight, add water to quench the reaction, extract all reaction solutions with dichloromethane, wash the organic phase with water, and finally combine the organic phases with anhydrous sulfuric acid. Dry with sodium, filter, evaporate the organic solvent to dryness, and purify the obtained product with a silica gel column. The mobile phase is dichloromethane:petroleum ether=1:4, finally obtaining 4.4mmol of monomer F1, yield: 88.0%. Dry under vacuum for use. MS(ASAP)=683.2

(6) Synthesis of monomer F2

The synthetic experimental route is shown in the figure below:

The synthesis steps are as follows:

a. The synthesis method is similar to that of the monomer F1, the yield: 61.4%. Vacuum dry for use. MS(ASAP)=210.1.

b. The synthesis method is similar to the synthesis method of monomer F1, the yield: 45.8%. Dry under vacuum for use. MS(ASAP)=208.1.

(7) Synthesis of monomer F3

The synthetic experimental route is shown in the figure below:

The synthesis steps are as follows:

a. The synthesis method is similar to that of the monomer F1, the yield: 60.5%. Vacuum dry for use. MS(ASAP)=408.1.

b. The synthesis method is similar to the synthesis method of the monomer F1, the yield: 67.4%. Dry under vacuum for use. MS(ASAP)=406.2.

(8) Synthesis of monomer F4

The synthetic experimental route is shown in the figure below:

The synthesis steps are as follows:

a. The synthesis method is similar to the synthesis method of monomer F1, the yield: 68.1%. Vacuum dry for use. MS(ASAP)=273.1.

b. The synthesis method is similar to the synthesis method of monomer F1, and the yield: 78.4%. Dry under vacuum for use. MS(ASAP)=271.2.

2. Synthesis of polymers

For the synthesis of high polymer, the main synthesis steps are as follows: taking the synthesis of P1 polymer as an example, under nitrogen protection, 0.10mmolE1, 0.40mmolF1 and 0.5molF5 monomers were dissolved in benzene solvent, and added with a syringe at the same time. 0.01 mmol 2,2-azobisisobutyronitrile (AIBN initiator), sealed, reacted at 60°C for 4 hours, when the reaction was completed, cooled to room temperature, and the polymer was precipitated with methanol. The precipitate was dissolved with tetrahydrofuran (THF) and then precipitated with methanol. so repeated

and vacuum drying to obtain a solid of polymer P1.

The synthesis steps for P2-P13 are similar to those of P1, the difference is that they contain vinyl monomers in different proportions. The monomers and proportions contained in P2-P13 are shown in the following table:

high polymer	E1	E2	E3	E4	E5	F1	F2	F3	F4	F5
P1	10							40		50
P2		10						40		50
P3			10					40		50
P4				10				40		50
P5					10			40		50
P6				10		40				50
P7					10	40				50
P8	10							40	15	35
P9				10		40			15	35
P10				10		40	15		10	35
P11					10	40	10		10	30
P10	15									85
P11		15								85
P12				15						85
P13					15					85

3. Fabrication and measurement of OLED devices

The preparation process of the OLED device using the above-mentioned high polymer will be described in detail below through specific examples. The structure of the OLED device is: ITO/HIL/HTL/EML/ETL/cathode, and the preparation steps are as follows:

a. Cleaning of ITO (indium tin oxide) conductive glass substrate: use various solvents (such as one or more of chloroform, acetone or isopropanol) to clean, and then perform ultraviolet ozone treatment;

b. HIL (hole injection layer, 60nm): 60nm PEDOT (polyethylenedioxythiophene, Clevios ^™ AI4083) was spin-coated in a clean room as HIL and treated on a hot plate at 180°C for 10 minutes ;

c. HTL (hole transport layer, 20 nm): TFB of 20 nm was formed by spin coating in a nitrogen glove box, and the solution used was a toluene solvent solution of TFB with a solubility of 5 mg/ml, followed by heating at 180°C. Plate treatment for 60 minutes;

Among them, TFB (H.W.SandsCorp.) is a hole transport material for HTL, and its structural formula is as follows:

d. EML (Organic Light Emitting Layer): EML was formed by spin coating in a nitrogen glove box, and the solution used was a polymer (P1-P9) added to a toluene solvent with a solution solubility of 10 mg/ml, followed by Treated on a hot plate at 180°C for 10 minutes; Table 2 lists the EML components and thicknesses of the devices;

Table II

device	HTL	EML	color	V@1knits[V]	Efficiency@1knits[Cd/A]
OLED1	TFB	P1(65nm)	blue	6.5	5.5
OLED2	TFB	P2(65nm)	blue	6.3	6.1
OLED3	TFB	P3(80nm)	blue	7.1	6.2
OLED4	TFB	P4(80nm)	green	4.5	62
OLED5	TFB	P5(80nm)	green	4.8	58
OLED6	TFB	P6(65nm)	green	7.0	41
OLED7	TFB	P7(65nm)	green	6.6	45
OLED8	TFB	P8(65nm)	blue	6.7	6.7
OLED9	TFB	P9(80nm)	green	6.4	56

e. Cathode: Ba/Al (2nm/100nm) is thermally evaporated in high vacuum (1× ^10-6mbar );

f. Encapsulation: The device was encapsulated with UV-curable resin in a nitrogen glove box.

The current-voltage and light-emitting (IVL) characteristics of each OLED device were characterized by characterizing the device while recording important parameters such as efficiency, lifetime and driving voltage. The performance of the OLED devices is summarized in Table 2. The FWHM of the emission spectrum of all OLEDs is less than 40 nm.

4. Preparation of Color Conversion Film

The polymer (P10-P13) was dissolved in a toluene solvent to prepare a solution with a solubility of 20 mg/ml, and a thin film of 100-300 nm was formed on the substrate by spin coating in a nitrogen glove box, and then heated at 180 °C. Plates were treated for 10 minutes. The obtained film can be used as a color conversion medium, wherein P10, P11 are blue light, P12 and P13 are green light, and the FWHM of the emission spectrum is all less than 40 nm.

The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are more specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the appended claims.

Claims (11)

1. A high polymer comprising repeating units as shown in chemical formula I:

   

   wherein n is greater than or equal to 1, X is selected from O, S, CR ¹ R ² , SiR ¹ R ² , NR ³ , and the repeating unit E is selected from the structural units of the following chemical formula (1) or (2):

   

   The symbols and signs used therein have the following meanings:

   The same or different Ar ¹ to Ar ³ are selected from aromatic or heteroaromatic having 5-24 ring atoms;

   The same or different Ar ⁴ to Ar ⁵ are selected from empty or aromatic or heteroaromatic with 5-24 ring atoms;

   When Ar ⁴ to Ar ⁵ are not empty, X _a , X _b are selected from N, C(R ⁹ ), Si(R ⁹ ); Y _a , Y _b are selected from B, P=O, C(R ⁹ ) , Si(R ⁹ );

   When Ar ⁴ to Ar ⁵ are empty, the corresponding X _a or Y _b is selected from N(R ⁹ ), C(R ⁹ R ¹⁰ ), Si(R ⁹ R ¹⁰ ), C=O, O, C=N (R ⁹ ), C=C(R ⁹ R ¹⁰ ), P(R ⁹ ), P(=O)R ⁹ , S, S=O or SO ₂ ;

   X ¹ , X ² are empty or a bridging group;

   R ¹ to R ¹⁰ may be the same or different selected substituents independently selected from H, D, -F, -Cl, Br, I, -CN, -NO ₂ , -CF ₃ , and have 1 to 20 C atoms straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy groups, or branched or cyclic alkyl, haloalkyl, alkoxy, thioalkane groups having 3 to 20 C atoms Oxy groups are either silyl groups, or substituted keto groups having 1 to 20 C atoms, or alkoxycarbonyl groups having 2 to 20 C atoms, or 7 to 20 Aryloxycarbonyl group of C atom, cyano group (-CN), carbamoyl group (-C(=O) _NH2 ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, Nitro groups, _CF3 groups, Cl, Br, F, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or 5 to 40 An aryloxy or heteroaryloxy group of 1 ring atoms, or an arylamino or heteroarylamino group with 5 to 40 ring atoms, a disubstituted unit at any position of the above substituents, or a combination of these systems, One or more of the substituent groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the group is bonded.
2. The high polymer according to claim 1, wherein the repeating structural unit E comprises a structural unit represented by the following chemical formula (1a) or (2a):

   

   Said symbols have the same meanings as in claim 1.
3. The high polymer according to claim 1, wherein the repeating structural unit E comprises a structural unit represented by one of the following chemical formulae (1b)-(1e) or (2b)-(2e):

   

   Said symbols have the same meanings as in claim 1.
4. The polymer according to claim 1, wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ in chemical formula (1) or (2) are independently selected from one of the following chemical structural formulas or a combination thereof :

   
5. The high polymer according to claim 1, wherein the repeating structural unit E is selected from the following structural units.

   
6. High polymer according to claim 1, has following chemical formula (II):

   

   The definition of Y is the same as the definition of X in claim 1, F is another organic functional group, n, m are integers greater than or equal to 1, and the other organic functional group is selected from the group having the following Functional groups: hole (also called hole) injection or transport, hole blocking, electron injection or transport, electron blocking, organic matrix, singlet emission (fluorescence emission), triplet emission (phosphorescence emission).
7. The high polymer according to claim 1, characterized in that, the full width at half maximum (FWHM) of its emission spectral line is less than or equal to 45 nm.
8. A mixture, comprising a polymer as claimed in claim 1, and at least another organic functional material, the at least another organic functional material is selected for hole (also known as hole) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injection or transport materials (EIM/ETM), electron blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescence emission body), triplet emitter (phosphorescent emitter).
9. A composition comprising a high polymer as claimed in claim 1, at least one organic solvent and/or an organic resin.
10. An organic optoelectronic device, comprising at least one polymer as claimed in claim 1 .
11. A polymerizable monomer having the general formula,

    

    It is characterized in that the unit E comprises a structural unit represented by chemical formulae (1)-(1e) or (2)-(2e).