WO2019128762A1 - Polymère contenant un groupe de liaison amide, mélange, composition et utilisation correspondante - Google Patents

Polymère contenant un groupe de liaison amide, mélange, composition et utilisation correspondante Download PDF

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WO2019128762A1
WO2019128762A1 PCT/CN2018/121557 CN2018121557W WO2019128762A1 WO 2019128762 A1 WO2019128762 A1 WO 2019128762A1 CN 2018121557 W CN2018121557 W CN 2018121557W WO 2019128762 A1 WO2019128762 A1 WO 2019128762A1
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polymer
organic
atoms
aromatic
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潘君友
杨曦
温华文
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广州华睿光电材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to the field of electroluminescent materials, and more particularly to an amide-containing group-containing polymer, mixture, composition and use thereof.
  • OLEDs Organic light-emitting diodes
  • Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter.
  • An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween.
  • the organic layer has a multilayer structure, and each layer contains 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.
  • Such an organic electroluminescence device 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, and excitons are formed when the injected holes meet the electrons. The excitons emit light when they transition back to the ground state.
  • Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.
  • general polymer optoelectronic materials have similar compatibility characteristics, namely polymer luminescent materials, hole injection/transport materials, electron injection/transport materials in toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene, tetrahydrofuran and the like. It has good solubility, so when preparing multi-layer, complex polymer light-emitting diodes by solution processing, there are problems such as interface miscibility and interface erosion. In order to solve the problem of interface erosion in solution processing, it is currently possible to develop a crosslinkable polymer photoelectric material by a cross-linking method, which has excellent solubility before crosslinking, and can be formed into a film by a solution processing method.
  • the crosslinking groups of the polymer side chains are chemically reacted with each other to form an insoluble and infusible three-dimensional interpenetrating network polymer, which has excellent solvent resistance and facilitates solution processing of subsequent functional layers.
  • Preparation J. Mater. Chem. 2008, 18, 4495.
  • the performance of processing OLEDs based on the solution of crosslinked polymers of these crosslinking groups has yet to be improved.
  • the existing crosslinkable polymers are all conjugated polymers, and their triplet energy levels are low. When used for phosphorescent green light, they do not play a good exciton blocking effect, causing a decrease in efficiency. Yes, the existing crosslinkable polymer itself has limited stability, resulting in a low lifetime of the OLED device.
  • o is the number of repetitions of the repeating unit, is an integer greater than or equal to 1;
  • Ar 1 and Ar 2 are each independently selected from aromatic, heteroaromatic aromatic or heteroaromatic groups having 5 to 50 ring atoms, said aromatic group, heteroaromatic group and non-aromatic group The group is optionally further substituted with one or more R 1 substituents;
  • T 1 and T 2 are each independently an amide group; and when a plurality of T 1 are present, a plurality of said T 1 are the same or different, and when a plurality of T 2 are present, a plurality of said T 2 are the same or different;
  • a, b are each independently 0 or 1, and at least one of a and b is 1;
  • a plurality of the R 1 are the same or different.
  • An amide bond group-containing mixture comprising at least one of the above-described amide bond group-containing polymers, and at least one other organic functional material selected from the group consisting of hole injection materials, hole transport Materials, electron transport materials, electron injecting materials, electron blocking materials, hole blocking materials, luminescent materials, host materials, and organic dyes.
  • a composition comprising at least one of the above-described amide bond group-containing polymers or the above-described amide bond group-containing mixture, and at least one organic solvent.
  • An organic electronic device comprising at least one of the above-described amide bond group-containing polymers or the above-described amide bond group-containing mixture.
  • the above amide bond group-containing polymer has a conjugated structural unit, it imparts rich optical and electrical properties to the polymer.
  • the polymer material undergoes chemical reaction cross-linking under heating to form an insoluble and infusible interpenetrating network polymer film, which has excellent solvent resistance and is suitable for fabricating complex multilayer organic electronic devices. specifically:
  • the amide bond group-containing polymer of the present invention wherein the conjugated structural unit imparts rich optical (photoluminescence, electroluminescence, photovoltaic effect, etc.), electrical (semiconductor characteristics, carrier transport) to the polymer Properties such as properties, etc., and its polymer properties have both good solubility and film forming properties. Under heating conditions, the polymer can undergo a chemical reaction to form a three-dimensional insoluble and infusible interpenetrating network polymer film with excellent solvent resistance.
  • the solution processing characteristics of the polymer can be utilized, and the polymer optoelectronic device can be prepared by solution processing such as inkjet printing, screen printing, spin coating, etc., and intermolecular crosslinking can be formed to form insoluble.
  • the molten three-dimensional interpenetrating polymer film has excellent solvent resistance and is advantageous for solution processing of multilayer polymer optoelectronic devices, especially organic electroluminescent devices.
  • the amide-bond-containing polymer of the present invention has a weak conjugate ability of an amide group, resulting in a polymer
  • the lowest unoccupied molecular orbital (LUMO) and triplet energy levels (E T ) have little effect as the degree of polymerization becomes larger, which is beneficial to the restriction of excitons in the luminescent layer, which is beneficial to the application in polymer optoelectronic devices. Especially for the application of hole transport materials.
  • FIG. 1 is a structural view 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), and 104 is a light-emitting layer, 105 It is an electron injection layer (EIL) or an electron transport layer (ETL), and 106 is a cathode.
  • HIL hole injection layer
  • HTL hole transport layer
  • ETL electron transport layer
  • ETL electron transport layer
  • the present invention provides a class of polymers containing amide bond groups and their use in organic electronic devices.
  • the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • the singlet states and the singlet states have the same meaning and are interchangeable.
  • the triplet state and the triplet state have the same meaning and are interchangeable.
  • composition and the printing ink, or ink have the same meaning and are interchangeable.
  • the polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer.
  • the high polymer also includes a dendrimer.
  • the conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp2 hybrid orbitals of C atoms.
  • Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene), the main chain thereof.
  • the C atom on it can also be replaced by other non-C atoms, and when the sp2 hybrid on the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer.
  • the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • the energy level structure of the organic material the triplet energy levels E T , HOMO, and LUMO play a key role.
  • the following is an introduction to the determination of these energy levels.
  • the HOMO and LUMO levels can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effect such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • 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 E T of organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or as described below in the examples.
  • the absolute values of HOMO, LUMO, E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and E T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • (HOMO-1) is defined as the second highest occupied orbital level
  • (HOMO-2) is the third highest occupied orbital level
  • (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 formula (I):
  • o is the number of repetitions of the repeating unit, is an integer greater than or equal to 1;
  • Ar 1 and Ar 2 are each independently selected from aromatic, heteroaromatic aromatic or heteroaromatic groups having 5 to 50 ring atoms, said aromatic group, heteroaromatic group and non-aromatic group The group is optionally further substituted with one or more R 1 substituents;
  • T 1 and T 2 are each independently an amide group; and when a plurality of T 1 are present, a plurality of said T 1 are the same or different, and when a plurality of T 2 are present, a plurality of said T 2 are the same or different;
  • a, b are each independently 0 or 1, and at least one of a and b is 1;
  • a plurality of the R 1 are the same or different.
  • said T 1 and T 2 comprise a structure as shown in formula (II):
  • R 3 has the same meaning as R 1 above.
  • said T 1 or T 2 contains one or more of the following structural formulas:
  • N1 represents an integer from 0-30.
  • the polymer according to the invention has a molecular weight Mw ⁇ 10000 g/mol, preferably ⁇ 50000 g/mol, more preferably ⁇ 100000 g/mol, more preferably ⁇ 150000 g/mol Preferably, it is ⁇ 200,000 g/mol.
  • each of Ar 1 and Ar 2 is independently selected from an aromatic group or a heteroaromatic group having 6 to 50 ring atoms, each occurrence; in a more preferred embodiment, Ar 1 and Ar 2 are each independently selected from an aromatic group or an aromatic hetero group having a ring number of 6 to 45; in a highly preferred embodiment, Ar 1 and Ar 2 are Each occurrence is independently selected from an aromatic group or a heteroaromatic group having a ring number of from 6 to 40; in a most preferred embodiment, Ar 1 and Ar 2 are each independently present at each occurrence. It is selected from an aromatic group or a heteroaromatic group having a ring number of 6 to 30. One or more of the groups may be further substituted.
  • An aromatic ring system or an aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • Heteroaromatic or heteroaromatic groups refer to hydrocarbyl groups (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems.
  • the heteroatoms are preferably selected from the group consisting of Si, N, P, O, S and/or Ge, particularly preferably selected from the group consisting of 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, a fused ring.
  • At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • an aromatic group or a heteroaromatic group includes not only an aromatic or heteroaromatic system, but also a plurality of aryl or heteroaromatic groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic groups for the purposes of this invention.
  • examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, hydrazine, hydrazine Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.
  • the Ar 1 has a larger energy gap ⁇ -conjugated structural unit, also called a Backbone Unit, preferably ⁇ 2.2 eV; more preferably ⁇ 2.5 eV; more preferably ⁇ 3.0 eV; most preferably ⁇ 3.5 eV.
  • the Ar 1 comprises one or more combinations of the following structural groups:
  • the polymer according to the present invention wherein Ar 1 or Ar 2 may be the same or different in multiple occurrences, is selected from the group consisting of a cyclic aromatic group, including benzene, biphenyl, Triphenyl, benzo, anthracene, anthracene and derivatives thereof; aromatic heterocyclic groups including triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran , benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, triazole, dioxin, Thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,
  • the polymer according to formula (I) wherein Ar 1 or Ar 2 when multiple occurrences, may be the same or differently selected from one or the following of the following structural groups; Combination of, which can be further arbitrarily replaced:
  • u is 1 or 2 or 3 or 4.
  • the conjugated polymer comprises at least one backbone structural unit.
  • the main chain structural unit generally has a larger energy gap ⁇ -conjugated structural unit, also called a Backbone Unit, and may be selected from a monocyclic or polycyclic aryl or heteroaryl group.
  • the conjugated polymer may contain two or more main chain structural units.
  • the content of the main chain structural unit is ⁇ 40 mol%, preferably ⁇ 50 mol%, more preferably ⁇ 55 mol%, most preferably ⁇ 60 mol%.
  • Ar 1 is a polymer backbone structural unit selected from the group consisting of benzene, biphenyl, triphenyl, benzo, anthracene, pyrene, oxazole, Carbazole, dibenzothiol, dithienocyclopentadiene, dithienothiolan, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran, benzothiophene, benzoselenophene and derivative.
  • Ar 1 is a polymer backbone structural unit selected from the group consisting of benzene, biphenyl, triphenyl, benzo, anthracene, pyrene, oxazole, Carbazole, dibenzothiol, dithienocyclopentadiene, dithienothiolan, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran,
  • the Ar 1 is selected from the group consisting of benzene, Biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, anthracene, diterpene, snail.
  • the polymers of the present invention have hole transport properties.
  • said Ar 2 has a smaller energy gap ⁇ -conjugated structural unit, preferably ⁇ 3.5 eV; more preferably ⁇ 3.2 eV; most preferably ⁇ 3.0 eV
  • the conjugated structure containing a small energy gap in the polymer allows the polymer to generate charges more easily under the action of an electric field.
  • the polymer according to the invention wherein Ar 2 is selected from the group having the hole transporting property, and the preferred hole transporting unit is selected from the group consisting of aromatic amines, triphenylamines, naphthylamines, thiophenes, carbazoles. , dibenzothiophene, dithienocyclopentadiene, dithienothiolan, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole And its derivatives.
  • Ar 2 has the structure represented by Chemical Formula 1:
  • Ar1, Ar2, and Ar3 can independently select the same or different forms when appearing multiple times.
  • Ar1 selected from a single bond, a mononuclear aryl group, a polynuclear aryl group, a mononuclear heteroaryl group or a polynuclear heteroaryl group, and this aryl or heteroaryl group may be substituted with other side chains.
  • Ar2 selected from mononuclear aryl, polynuclear aryl, mononuclear heteroaryl or polynuclear heteroaryl, this aryl or heteroaryl may be substituted by other side chains.
  • Ar3 selected from mononuclear aryl, polynuclear aryl, mononuclear heteroaryl or polynuclear heteroaryl, this aryl or heteroaryl may be substituted by other side chains. Ar3 may also be linked to other moieties in Formula 1 via a bridging group.
  • n selected from 1, 2, 3, 4, or 5.
  • the structural unit represented by the preferred chemical formula 1 is the chemical formula 2
  • Ar4, Ar6, Ar7, Ar10, Ar11, Ar13, Ar14: are defined as Ar2 in Chemical Formula 1,
  • Ar5, Ar8, Ar9, Ar12: are defined as Ar3 in Chemical Formula 1.
  • Ar1-Ar14 in Chemical Formula 1 and Chemical Formula 2 is preferably selected from the group consisting of phenylene, naphthalene, anthracene, fluorene, spirobifluorene, hydrazine ( Indenofuorene), phenanthrene, thiophene, pyrrole, carbazole, binaphthalene, dehydrophenanthrene, and the like.
  • R is selected from H, or D, or an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 10 ring atoms.
  • the plurality of Rs are the same or different.
  • HTM hole transport material small molecule hole transport material
  • Suitable HTM materials may optionally include compounds having the following structural units: phthlocyanine, porphyrine, amine, aromatic amine, triarylamine, thiophene, thiophene. (fused thiophene) (such as dithienothiophene and dibenzothiphene), pyrrole, aniline, carbazole, indolocarbazole, and their derivatives Things.
  • the Ar 2 comprises one or more combinations of the following structural groups:
  • each occurrence of Ar 3 -Ar 11 is independently selected from an aromatic or heteroaromatic ring system of 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms a group, or a non-aromatic group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups may be further substituted;
  • each occurrence of Ar 3 -Ar 11 is independently selected from an aromatic or heteroaromatic ring system of 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms. a group, or a non-aromatic group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups may be further substituted;
  • the polymers of the present invention have electron transport properties.
  • the polymer according to the invention wherein Ar 2 is selected from units having electron transport properties, and the preferred electron transport unit may be selected from pyrazole, imidazole, triazole, oxazole, thiazole , oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine, oxadiazines, hydrazine, benzimidazole, carbazole, Indoxazine, bisbenzoxazoles, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, Phenoxazines,
  • ETM electron transport materials
  • ETM can be used as the unit of the invention with electron transport properties.
  • ETM is sometimes referred to as an n-type organic semiconductor material.
  • 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 the group consisting of tris(8-hydroxyquinoline)aluminum (AlQ3), phenazine, Phenanthroline, Anthracene, Phenanthrene, Fluorene, and Bifluorene, Spiro-bifluorene, Phenylene-vinylene, triazine, triazole, imidazole, pyrene, Perylene, Trans-Indenofluorene, cis-Indenon fluorene, Dibenzol-indenofluorene, Indenonaphthalene, Benzanthracene and their derivatives .
  • AlQ3 tris(8-hydroxyquinoline)aluminum
  • phenazine Phenanthroline
  • Anthracene Phenanthrene
  • Fluorene and Bifluorene
  • Spiro-bifluorene Phenylene-vinylene
  • triazine triazole
  • the Ar 2 having electron transporting property may be selected from the group having any one of the following formulas:
  • t represents an integer from 1-20;
  • R 7 is independently selected from the group consisting of hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl , aryl or heteroaryl;
  • Each occurrence of X 1 -X 8 is independently selected from CR 8 or N, and at least one is N;
  • Ar 12 -Ar 16 has the same meaning as Ar 3 ;
  • R 8 has the same meaning as R 1 .
  • the polymer of the present invention contains a crosslinkable group; the crosslinkable group is preferably selected from a linear or cyclic alkenyl group, a linear dienyl group, an alkynyl group.
  • the crosslinkable group is selected from one of the following structures:
  • the dotted line represents the position at which the crosslinking monomer is bonded to a functional group on other monomers or monomers in the polymer, and t and t1 represent an integer greater than or equal to zero.
  • Ar 17 comprises an aromatic ring system or a heteroaromatic ring system having 5 to 40 ring atoms
  • R 9 to R 11 are independently selected from the group consisting of H, D, F, CN, alkyl chain, fluoroalkyl chain, aromatic ring, aromatic heterocyclic ring, amino group, silicon group, and Mercapto, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl chain, deuterated partially fluorinated alkyl chain, deuterated aromatic ring, deuterated aromatic Heterocyclic, deuterated amino, deuterated silyl, deuterated indenyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy, deuterated siloxane, deuterated silyloxy Base, crosslinkable group.
  • the adjacent R 9 , R 10 , R 11 may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other or a ring bonded to the group;
  • crosslinkable groups can be present in the polymer in a variety of forms.
  • the crosslinkable group is substituted in the form of a substituent for each repeating unit on the polymer, such as the following formula:
  • Q is a crosslinkable group as described above, Ar is a repeating unit on the polymer, and x is a mole fraction
  • the crosslinkable group is attached to Ar 1 .
  • the crosslinkable group is attached to T 1 or T 2 .
  • the crosslinkable group is attached to Ar 2 .
  • the molar fraction x of the repeating unit comprising the crosslinkable group is: 0.02 ⁇ x ⁇ 0.30, preferably 0.05 ⁇ x ⁇ 0.25, more preferably 0.08 ⁇ x ⁇ 0.20, Preferably, it is 0.10 ⁇ x ⁇ 0.18.
  • the number of moles of Ar 2 having a hole transporting property is yh, wherein 0.02 ⁇ yh ⁇ 0.30, preferably 0.05 ⁇ yh ⁇ 0.25, more Preferably, 0.08 ⁇ yh ⁇ 0.20, preferably 0.10 ⁇ yh ⁇ 0.18.
  • the number of moles of Ar 2 having electron transport properties is ye, wherein 0.02 ⁇ ye ⁇ 0.30, preferably 0.05 ⁇ ye ⁇ 0.25, more preferably 0.08 ⁇ ye ⁇ 0.20, preferably 0.10 ⁇ ye ⁇ 0.18.
  • the best eV is ⁇ 0.5eV.
  • HOMO indicates that the polymer has the highest occupied orbital
  • HOMO-1 indicates that the polymer has the second highest occupied orbit.
  • the polymer according to the invention has a higher LUMO, preferably LUMO ⁇ -2.7 eV, more preferably ⁇ -2.6 eV, more preferably ⁇ -2.5 eV, most preferably ⁇ -2.4 eV.
  • the polymer according to the invention has a lower HOMO, preferably HOMO ⁇ -5.0 eV, more preferably ⁇ -5.1 eV, most preferably ⁇ - 5.2 eV.
  • the polymer according to the invention has a relatively large triplet energy level E T , preferably E T ⁇ 2.5 eV, more preferably ⁇ 2.6 eV, most preferably ⁇ 2.7 eV.
  • the polymer according to the invention is a conjugated polymer.
  • a is 1, b is 1, o is 1, and p is 1.
  • the polymer has a structural unit represented by any one of the following formulas (II-1) to (II-10):
  • R 11 , R 12 and R 13 have the same meaning as R 3 ;
  • 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 5 to 30 substituted or unsubstituted a non-aromatic group of a ring atom;
  • L does not exist, or is CH 2 ;
  • W is O or S
  • a in the formula (II-1) to the formula (II-10) is selected from the group consisting of:
  • Y is CR 14 R 15 , SiR 14 R 15 , NR 14 , O, S or Se;
  • R 14 and R 15 are each independently H, C1-C20 alkyl, vinyl,
  • R 11 is H, C1-C20 alkyl, vinyl, ethynyl, When there are a plurality of R 11 , a plurality of the R 11 are the same or different;
  • R 12 and R 13 are each independently selected from the group consisting of H, C1-C20 alkyl, 3-10 membered cycloalkyl, phenyl or
  • R 12 or R 13 When a plurality of said R 12 or R 13 are present, a plurality of said R 12 or R 13 are the same or different.
  • the above polymer has a structural unit represented by the formula (III-1)
  • R 14 and R 15 are each independently H or a C1-C10 alkyl group
  • R 11 is H, C1-C20 alkyl or vinyl; when a plurality of R 11 are present, a plurality of said R 11 are the same or different;
  • n 1 or 2.
  • the above polymer has a structure represented by the formula (III-2)
  • R 16 and R 17 are each independently selected from: R 11 is H, C1-C6 alkyl or vinyl, and the R 16 and R 17 are not the same.
  • the invention further relates to a process for the synthesis of a polymer according to formula (I), wherein the reaction is carried out using a starting material containing a reactive group.
  • the polymer may pass through at least one monomer having a lactam, or an amine group and an acid group (including a carboxylic acid, an acid halide, etc.), or at least two kinds of a diamine and a dibasic acid group respectively (including a carboxylic acid)
  • the monomer of the acid halide or the like is obtained by polycondensation.
  • the polymer of the present invention may be a homopolymer or a copolymer.
  • the copolymer may be a disordered, alternating, block, comb or dendritic copolymer.
  • the processes used to form polymers of these various structures are well known in the art, such as George Odian (John Wiley & Sons, New York, NY, 1991), Principles Of Polymerization, Third Edition; Chemical Reactions by M. Lazer et al. Of Natural and Synthetic Polymers; and Chemical Reactions on Polymers (1988) by Benham and Kinstle.
  • the synthesis method of 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.
  • the above polymer has a glass transition temperature (Tg) ⁇ 100 ° C, preferably ⁇ 120 ° C, more preferably ⁇ 140 ° C, more preferably ⁇ 160 ° C, and most preferably ⁇ 180 ° C. .
  • Tg glass transition temperature
  • the molecular weight distribution (PDI) of the above polymer preferably ranges from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably from 1 to 2, most preferably It is 1 to 1.5.
  • the weight average molecular weight (Mw) of the above polymer is preferably in the range of 10,000 to 1,000,000; more preferably 50,000 to 500,000; more preferably 100,000 to 400,000, still more preferably It is 150,000 to 300,000, and most preferably 200,000 to 250,000.
  • the present invention also provides a mixture comprising at least one of the above-described polymers, and at least one other organic functional material, the at least another organic functional material being selectable from a hole injecting material (HIM), hole transport material (HTM), electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), luminescent material (Emitter), host material ( Host) and organic dyes.
  • HIM hole injecting material
  • HTM hole transport material
  • ETM electron transport material
  • EIM electron injecting material
  • EBM electron blocking material
  • Emitter hole blocking material
  • Host host material
  • organic dyes organic dyes.
  • organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the mixture comprises a polymer according to the invention, and a fluorescent illuminant (or singlet illuminant).
  • the polymer according to the invention may be used herein as a host, wherein the weight percentage of the fluorescent illuminant is ⁇ 15% by weight, preferably ⁇ 12% by weight, more preferably ⁇ 9% by weight, still more preferably ⁇ 8% by weight, most preferably ⁇ 7wt %.
  • the mixture comprises a polymer in accordance with the present invention, and a TADF material.
  • the mixture comprises a polymer according to the invention, and a phosphorescent emitter (or triplet emitter).
  • the polymer according to the invention may be used herein as the host, wherein the weight percentage of the phosphorescent emitter is ⁇ 30% by weight, preferably ⁇ 25% by weight, more preferably ⁇ 20% by weight, most preferably ⁇ 18% by weight.
  • the mixture comprises a polymer according to the invention, and an HTM material.
  • the singlet emitter, triplet emitter and TADF material are described in more detail below (but are not limited thereto).
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindoles and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847, and disclosed in US Pat. No. 7,233,019, KR2006-0006760 A quinone triarylamine derivative.
  • the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • Further preferred singlet emitters are selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.
  • More preferred singlet emitters may be selected from the derivatives of hydrazine, such as those disclosed in US2013175509A1; triarylamine derivatives of hydrazine, such as triarylamine derivatives of hydrazine containing dibenzofuran units disclosed in CN102232068B; A triarylamine derivative of hydrazine having a specific structure, as disclosed in CN105085334A, CN105037173A.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L)u, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and u is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.
  • the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene.
  • a quinolinol derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;
  • Ar 1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal.
  • Ar 2 may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar 1 and Ar 2 are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group; L' may be the same or different at each occurrence, and is a bidentate chelate auxiliary ligand, preferably Is a monoanionic bidentate chelate ligand; q can be 0, 1, 2 or 3, preferably 2 or 3; p can be 0, 1, 2 or 3, preferably 1 or 0.
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below:
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ E st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondarily ⁇ Est ⁇ 0.25 eV, more preferably ⁇ Est ⁇ 0.20 eV, and most preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following 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, et. al. Chem.
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the polymer according to the invention has a solubility in toluene of > 5 mg/ml, preferably > 7 mg/ml, most preferably > 10 mg/ml at 25 °C.
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic a compound, or a borate or phosphate compound, or a mixture of two or more solvents.
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents.
  • aromatic or heteroaromatic solvents suitable for the present invention are, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene.
  • aromatic ketone solvents suitable for the present invention are, but are not limited to, 1-tetralone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy Tetrendanone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.;
  • aromatic ether-based solvents suitable for the present invention are, but are not limited to, 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H -pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxy Toluene, 4-ethyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methyl Oxynaphthalene, diphenyl ether
  • the at least one organic solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-fluorenone, 3-fluorenone, 5-fluorenone, 2 - anthrone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, anthrone, phorone, isophorone, di-n-pentyl ketone, etc.; or an aliphatic ether
  • the at least one organic solvent may be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, benzene. Alkyl formate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide, alkyl oleate, and the like. Particularly preferred are octyl octanoate, diethyl sebacate, diallyl phthalate, isodecyl isononanoate.
  • the solvent may be used singly or as a mixture of two or more organic solvents.
  • a composition according to the present invention comprises a polymer or mixture as described above and at least one organic solvent, which may further comprise another organic solvent, and another 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, decalin
  • the solvent particularly suitable for the present invention is a solvent having Hansen solubility parameters in the following ranges:
  • ⁇ d (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2 , especially in the range of 18.5 to 21.0 MPa 1/2 ;
  • ⁇ p polar forces in the range of 0.2 ⁇ 12.5MPa 1/2, especially in the 2.0 ⁇ 6.0MPa 1/2;
  • the organic solvent is selected in consideration of its boiling point parameter.
  • the organic solvent has a boiling point of ⁇ 150 ° C; preferably ⁇ 180 ° C; more preferably ⁇ 200 ° C; more preferably ⁇ 250 ° C; optimally ⁇ 275 ° C or ⁇ 300 ° C.
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the organic solvent can be evaporated from the solvent system to form a film comprising the functional material.
  • the invention further relates to the use of a composition as a printing ink for the preparation of organic electronic devices, particular preference being given to a preparation process by printing or coating.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.
  • Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the invention further relates to an organic electronic device comprising at least one polymer or mixture as described above.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.
  • the electroluminescent device has an electron transport layer or a hole transport layer comprising a polymer or mixture as described above.
  • the invention further comprises a method for preparing a functional layer comprising the polymer of the invention in an organic electronic device, comprising at least the following steps:
  • the first step dissolving the polymer of the present invention in an organic solvent or a mixed solvent to prepare a solution;
  • the second step coating the solution onto a functional layer of the device by printing or coating, wherein the printing or coating method can be selected from, but not limited to, inkjet printing, printing (Nozzle Printing) ), typography, screen printing, dip coating, spin coating, knife coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit extrusion Pressure coating, etc.;
  • the printing or coating method can be selected from, but not limited to, inkjet printing, printing (Nozzle Printing) ), typography, screen printing, dip coating, spin coating, knife coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit extrusion Pressure coating, etc.;
  • the third step heat-treating the obtained film at a temperature of at least 100 degrees Celsius, optionally by adding ultraviolet light to cause cross-linking reaction.
  • the crosslinked cured film is washed with an organic solvent to remove residual compounds which are not crosslinked and cured.
  • the resulting crosslinked cured film (after solvent cleaning) has a thickness of at least 50%, preferably at least 60%, more preferably at least 70%, preferably at least 70%, prior to crosslinking. At least 85%.
  • a substrate an anode, at least one light-emitting layer, and a cathode are included.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, 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.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-na
  • the anode can 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 a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples 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.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2 /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 process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further include other 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), and a hole blocking layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the light-emitting device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the invention further relates to the use of an electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • reaction was quenched by the addition of water, extracted with ethyl acetate, and the organic phase was evaporated to remove the solvent, and the mixture was applied to silica gel to obtain the product intermediate 4, weight 2.95 g, yield 76%.
  • reaction was quenched by the addition of water, extracted with ethyl acetate, and the organic phase was evaporated to remove the solvent, and the mixture was applied to silica gel to obtain a product intermediate 8, weight 3.69 g, yield 83%.
  • intermediate 3 (733 mg, 1 mmol), intermediate 7 (119 mg, 0.3 mmol) and intermediate 9 (298 mg, 0.7 mmol) were added to a 25 mL reaction flask, and dissolved in 10 ml of DMAc. The solution was poured into a large amount of water, and the precipitate was filtered, washed with methanol and acetone, and dried in vacuo to give a polymer P.
  • the organic small molecule energy structure can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • TD-SCF/DFT/Default Spin/B3PW91 the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the energy structure of the polymer can be obtained by calculating the trimer.
  • the compound P1, the trimer M1-M2-M1 and/or M2-M1-M2 obtained by polymerizing the monomers M1 and M2 shown below are used to calculate the energy level in which the alkyl chain is substituted with a methyl group. .
  • the HOMO and LUMO energy levels calculated above are calculated according to the following calibration formula, and S1 and T1 are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 09W, and the unit is eV.
  • H1 is a co-host material, and its synthesis is referred to the Chinese patent of CN201510889328.8; H2 is a co-host material, and its synthesis refers to the patent WO201034125A1; E1 is a phosphorescent guest, and its synthesis refers to the patent CN102668152; Comp A to Comp C and Poly-TFB is a device HTL comparative material in which the synthesis of Comp A, Comp B and Comp C is similar to that of a similar structural compound of this patent; Poly-TFB (CAS: 223569-31-1) is purchased from Lumtec.Corp.
  • OLED-Ref The device structure of the OLED device (OLED-Ref) is: ITO/PEDOT: PSS (80 nm) / Poly-TFB (20 nm) / EML / cathode; OLED device (OLED-Ref) preparation steps are as follows:
  • ITO transparent electrode (anode) glass substrate cleaning ultrasonic treatment with 5% Decon90 cleaning solution for 30 minutes, then ultrasonic cleaning with deionized water several times, then ultrasonic cleaning with isopropanol, nitrogen drying; in oxygen plasma Under treatment for 5 minutes to clean the ITO surface and enhance the work function of the ITO electrode;
  • All devices are packaged in a UV glove box with UV curable resin and glass cover.
  • OLED-1 to OLED-3 and OLED-A to OLED-C are prepared as above, but in the preparation of the HTL layer, P1 to P3 and Comp A to Comp C are used instead of Poly-TFB, respectively. After cross-linking, the solution was washed twice with toluene and the film thickness was measured.
  • the current-voltage characteristics, luminous intensity and external quantum efficiency of the device were measured by a Keithley 236 current-voltage-measurement system and a calibrated silicon photodiode.
  • the efficiency is particularly improved compared to other comparative device properties. This may be due to two reasons.
  • the amide bond group-containing polymer HTM according to the present invention has a higher triplet energy level, thereby having a better blocking effect on the triplet state.
  • the amide bond group-containing polymer has good solubility and is suitable for solution processing, and the insolubility after cross-linking curing is also suitable for subsequent processing.

Abstract

L'invention concerne un polymère contenant un groupe de liaison amide, un mélange, une composition et un dispositif électronique organique le comprenant et une utilisation correspondante. Le polymère comprend une structure de squelette, reliée par l'intermédiaire d'une liaison amide, et un groupe de chaîne latérale fonctionnelle. Le polymère comprend en outre un groupe réticulable, peut être réticulé dans des conditions de chauffage pour former un film polymère insoluble et infusible, possède une excellente résistance aux solvants et est approprié pour produire un dispositif électronique organique multicouche complexe au moyen d'un traitement en solution. La présente invention concerne en outre l'utilisation du polymère dans des dispositifs optoélectroniques, tels que des transistors à effet de champ, organiques, des diodes électroluminescentes organiques, des cellules solaires polymères et des cellules solaires de type pérovskite.
PCT/CN2018/121557 2017-12-28 2018-12-17 Polymère contenant un groupe de liaison amide, mélange, composition et utilisation correspondante WO2019128762A1 (fr)

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