Patent Description:
Since the invention of organic light-emitting diodes (OLEDs), OLEDs have showed great potential in applications of optoelectronic devices (such as flat-panel displays and general lighting) because of the diversity in organic synthesis, relative low manufacturing costs, and excellent optical and electrical properties of organic/polymeric semiconductive materials.

To develop high-efficiency OLED devices, it is critical to inject electrons and holes from cathode and anode, repectively. Therefore, efficient OLED devices usually adopt a multi-layer device structure, that is, comprising one or more hole-transport/injection layers, or electron-transport/injection layers, in addition to the light-emitting layer. Accordingly, in addition to developement of excellent light-emitting materials, the development of excellent electron-transport/injection materials and hole-transport/injection materials is also critical for obtaining high-efficiency OLEDs (<NPL>; <NPL>; <NPL>).

It is easy to obtain multi-layer and complex high-efficiency OLEDs by vacuum evaporation, but it is difficult to realize large-scale application due to the expensive, time-consuming and wasteful materials. In contrast, solution processing OLEDs may be advantageously widely used in the preparation of large-area flexible devices with low-cost ink jet printing, printing, and other solution processs, and therefore are promising in a wide range of applications and great commercial value. As typical organic photoelectric materials have similar solubility, that is, organic/polymer light-emitting materials, hole-injection/transport materials, electronic injection/transport materials have good solubility in solvents such as toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene and tetrahydrofuran, therefore, there are problems of miscibility and erosion of interfaces when using the solution process to prepare multi-layer, complex OLEDs. For example, when preparing polymers or small-molecule light-emitting layers using solution process, the solvent used may dissolve the underlying hole-transport layer, causing problems such as miscibility and erosion of interfaces (<NPL>; <NPL>).

When conventional crosslinking groups, such as perfluorocyclobutane, styrene, oxetane, siloxane, acrylate and benzocyclobutene, are used in modification of conjugated polymers, cross linking reaction of the crosslinking groups perfluorocyclobutane (<NPL>), styrene(<NPL>), oxetane(<NPL>. ), siloxane(<NPL>), acrylate(<NPL>), and benzocyclobutene(<NPL>. ) can induced under conditions such as illumination, heating, etc, to form an insoluble and infusible film of interpenetrating polymer network with excellent solvent resistance so that the problems such as miscibility and erosion of interfaces are prevented (<CIT>, <CIT>).

However, the performance of solution-process OLEDs based on the cross-linked polymer of these crosslinking groups has yet to be improved.

Therefore, there is an urgent need for development of new high-performance cross-linkable polymeric electron-transport material.

<CIT> discloses crosslinkable substituted fluorene compounds; oligomers and polymers prepared from such crosslinkable compounds; films and coatings; and multilayer electronic devices comprising such films. <CIT> discloses crosslinkable arylamine compounds; oligomers and polymers prepared from such crosslinkable arylamine compounds; films and coatings; and multilayer electronic devices comprising such films. <CIT> discloses an organic photoelectric conversion element with high voltage at the time of photoelectric conversion. <CIT> discloses a polymer light-emitting device comprising a cathode, an anode, and a functional layer containing a polymer compound and a light-emitting layer containing an organic polymer light-emitting compound arranged between the cathode and the anode. <CIT> discloses preparation and application of a signal launch type mercury ion optical probe based on an arylamine/carbazole containing fluorescent polymer. <CIT> discloses a charge transporting semi-conducting material comprising: a) optionally at least one electrical dopant, and b) at least one cross-linked charge-transporting polymer comprising <NUM>,<NUM>,<NUM>-triazole cross-linking units, a method for its preparation and a semiconducting device comprising the charge transporting semi-conducting material. <CIT> discloses an organic electronic component having a cross-linked organic-electronic functional layer and alkinylether usable for production of said component. <NPL> discloses a type of triphenylamine-based conjugated polymer with cyano-containing chromophore in side chain, poly[(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-co-N-<NUM>-(<NUM>,<NUM>,<NUM>,<NUM>-tetracyanobuta-<NUM>,<NUM>-dienyl)-<NUM>,<NUM> ' -triphenylamine] (P3) was successfully synthesized by catalyst-free and efficient click reaction between poly[(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-co-N-<NUM>-ethynyl-<NUM>,<NUM>' -triphenylamine] (P2) and tetracyanoethylene (TCNE). <NPL> discloses a novel carbazole-based conjugated polymer with tethered acetylenes, poly [(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-(N-octyl-<NUM>,<NUM>-carbazole)]-co-[(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-(N-<NUM>-phe nylacetylene)-<NUM>,<NUM>-carbazole)] (P-<NUM>), was successfully synthesized through the desilylation of triisopropylsilyl (TIPS) protected precursor polymer, poly [(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-(N-octyl-<NUM>,<NUM>-carbazole)]-co-[(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-(N-<NUM>-triis opropylsilyl-phenylacetylene)-<NUM>,<NUM>-carbazole)] (P-<NUM>). <NPL> discloses a kind of triphenylamine-based conjugated polymer with simple structure, poly(<NUM>,<NUM>-dioctyl)-<NUM>,<NUM>-fluorene-co-N-<NUM>-phenylethenyl-<NUM>,<NUM> ' -triphenylamine (PFT-PE), was successfully synthesized via Suzuki coupling reaction. <NPL>) discloses preparation of mercury ion-optical probe based on conjugated polymers.

The invention is set out in the appended set of claims <NUM>-<NUM>. In one aspect of the present disclosure, there is provided a conjugated polymer containing an ethynyl crosslinking group; a mixture, a formulation, and an organic electronic device containing the same; and uses thereof. The conjugated polymer material may have a conjugated backbone structure and a functionalized ethynyl crosslinking group as side chain. Since the polymer has a conjugated backbone structure, the polymer is endowed with various optical and electrical properties. The conjugated polymer material may be cross-linked under heating to form an insoluble and infusible film of interpenetrating polymer network with excellent solvent resistance and is suitable for making complex multilayer organic electronic devices. The conjugated polymer may be used in optoelectronic devices such as organic light emitting diodes, polymer solar cells, organic field effect transistors, perovskite solar cells, improving device performance.

The conjugated polymer containing an ethynyl crosslinking group according to one aspect of the present disclosure may have the following structure (Chemical Formula <NUM>):
<CHM>
wherein, x and y are mole percentages which are greater than <NUM> and x + y = <NUM>;
<CHM>
is
<CHM>
and Ar1 is selected from the group consisting of benzene, thiophene, carbazole, indenofluorene, and indolocarbazole, and Ar1 is optionally substituted with any one group selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, or a combination thereof.

The present disclosure also provides a mixture which may comprise the above-described conjugated organic polymer and at least another organic functional material that is any one selected from the group consisting of a hole-injection material (HIM) , a hole-transport material (HTM) , an electron-transport material (ETM) , an electron-injection material (EIM) , an electron-blocking material (EBM) , a hole-blocking material (HBM) , a light-emitting material (Emitter) , and a host material (Host) , and the like.

The present disclosure also provides a formulation useful as a printing ink, which may comprise a conjugated polymer according to one aspect of the present disclosure or a mixture thereof, and at least one organic solvent.

The present disclosure further provides an organic electronic device which may comprise the conjugated organic polymer or a combination thereof, and the use thereof.

Compared with the prior art, the polymer material of the present disclosure has the following advantages:.

In one aspect of the present disclosure, there is provided a conjugated polymer containing an ethynyl crosslinking group and its use. The conjugated polymer material has a conjugated backbone structure and a functionalized ethynyl crosslinking group as side chain. The present disclosure will now be described in greater detail with reference to the accompanying drawings so that the purpose, technical solutions, and technical effects thereof are more clear and comprehensible. It is to be understood that the specific embodiments described herein are merely illustrative of, and are not intended to limit, the disclosure.

The present disclosure provides a conjugated polymer containing an ethynyl crosslinking group, having the following structure:
<CHM>
wherein, x and y are mole percentages and x + y = <NUM>; Ar1 and Ar2 in multiple occurences are the same or different and independently selected from an aryl or a heteroaryl group; and, R3 is a linking group.

As used herein, the term "small molecule" refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repetitive structure in small molecules. The molecular weight of the small molecule is no greater than <NUM>/mol, more preferably no greater than <NUM>/mol, and most preferably no greater than <NUM>/mol.

As used herein, the term "polymer" includes homopolymer, copolymer, and block copolymer. In addition, in the present disclosure, the polymer also includes dendrimer. The synthesis and application of dendrimers are described in <NPL>.

The term "conjugated polymer" as defined herein is a polymer whose backbone is predominantly composed of the sp2 hybrid orbital of carbon (C) atom. Some known non-limiting examples are: polyacetylene and poly (phenylene vinylene), on the backbone of which the C atom can also be optionally substituted by other non-C atoms, and which is still considered to be a conjugated polymer when the sp2 hybridization on the backbone is interrupted by some natural defects. In addition, the conjugated polymer in the present disclosure may also comprise aryl amine, aryl phosphine and other heteroarmotics, organometallic complexes, and the like.

In the present disclosure, the terms such as polymerid, polymeride, and polymer have the same meaning and are interchangeable in use.

In some embodiments, the polymers described in one aspect of the disclosure have a molecular weight (Mw) of no smaller than <NUM>/mol, more preferably no smaller than <NUM>/mol, more preferably no smaller than <NUM>/mol, and most preferably no smaller than <NUM>/mol.

In some preferred embodiments, the polymers described in one aspect of the disclosure are provided, wherein Ar1 and Ar2 are the same or different in multiple occurences and independently selected from any one of the following structural groups: an cyclic aromatic group, including any one of benzene, biphenyl, triphenyl, benzo, fluorene, indenofuorene, and derivatives thereof; and, a heterocyclic aromatic group, including triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole, benzimidazole, indoxazine, bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, and the like, or a combination thereof, or a combination thereof.

In some embodiments, the Ar1, Ar2 cyclic aryl groups and heterocyclic aryl groups may be further optionally substituted, wherein the substituents may be hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, or a combination thereof.

Typically, the conjugated polymer comprises at least one backbone structural unit. The backbone structural unit is typically a π-conjugated structural unit with relatively large energy gap, also referred to as backbone unit, which may be selected from monocyclic or polycyclic aryl or heteroaryl. In the present disclosure, the conjugated polymer may comprise two or more backbone structural units. Typically, the content of the backbone structural unit may be no smaller than <NUM> mol%, more preferably no smaller than <NUM> mol%, more preferably no smaller than <NUM> mol%, and most preferably no smaller than <NUM> mol%.

In a preferred embodiment, the polymer according to one aspect of the disclosure is provided, wherein Ar1 may be a polymer backbone structural unit that is any one selected from the group consisting of benzene, biphenyl, triphenyl, benzo, fluorene, indenofuorene, carbazole, indolocarbazole, dibenzosilole, dithienocyclopentadiene, dithienosilole, thiophene, anthracene, naphthalene, benzodithiophene, benzofuran, benzothiophene, benzene And selenophene and its derivatives, or a combination thereof.

"Polymer backbone" refers to a chain having the largest number of chain units or repeating units in a polymer chain with a branched (side chain) structure.

In some embodiments, the polymers of the present disclosure have hole-transport properties.

In a preferred embodiment, the polymer according to one aspect of the disclosure is provided, wherein Ar2 may be selected from units having hole-transport properties, and a hole-transport unit may be preferably any one selected from the group consisting of aromatic amines, triphenylamine, naphthylamine, thiophene, carbazole, dibenzothiophene, dithienocyclopentadiene, dithienosilole, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolecarbazole, and their derivatives, or a combination thereof.

In another preferred embodiment, Ar2 may have the structure represented by Chemical Formula <NUM>:
<CHM>
wherein Ar<NUM>, Ar<NUM>, Ar<NUM> in multiple occurences are independently the same or different:.

The preferred structural unit represented by Chemical Formula <NUM> is Chemical Formula <NUM>
<CHM>
wherein.

Ar<NUM>-Ar<NUM> in Chemical Formula <NUM> and Chemical Formula <NUM> may be preferably selected from the group consisting of phenylene, naphthalene, anthracene, fluorene, spirobifluorene, indenofuorene, phenanthrene, thiophene, pyrrole, carbazole, binaphthalene, dehydrophenanthrene, and the like, or a combination thereof.

Particularly preferred alternatives of the structural units represented by Chemical Formula <NUM> and Chemical Formula <NUM> are listed in Table <NUM>. Each of these compounds may be optionally substituted with one or more substituents, and R is a substituent.

In another preferred embodiment, Ar2 may have a structure represented by Chemical Formula <NUM>.

(D<NUM>)n1-(Ar<NUM>)n2-(D<NUM>)n3-(Ar<NUM>)n4     Chemical Formula <NUM>.

wherein
D<NUM> and D<NUM> may be independently the same or different in multiple occurrences and may be selected from any of the following functional groups or any combinations thereof: thiophene, selenophene, thieno[<NUM>,3b]thiophene, thieno [<NUM>,2b] thiophene, dithienothiophene, pyrrole, and aniline, all of which functional groups may be optionally substituted by any group below: halogen, -CN, -NC, -NCO, -NCS, -OCN, SCN, C(=O)NR<NUM>R<NUM>, -C(=O)X, -C(=O)R<NUM>, -NH<NUM>, -NR<NUM>R<NUM>, SH, SR<NUM>, -SO<NUM>H, -SO<NUM>R<NUM>, -OH, -NO<NUM>, -CF<NUM>, -SF<NUM>, silyl or carbyl or hydrocarbyl having <NUM> to <NUM> C atoms, wherein R<NUM> and R<NUM> are substituent groups.

Ar<NUM> and Ar<NUM> may be independently selected from the same or different forms in multiple occurrences and may be selected from mononuclear or polynuclear aryl or heteroaryl and may be optionally fused to their respective adjacent D<NUM> and D<NUM>.

n1-n4 may be independently selected from an integer from <NUM> to <NUM>.

Preferably, Ar<NUM> and Ar<NUM> in the materials represented by Chemical Formula <NUM> are selected from phenylene, naphthalene, anthracene, fluorene, spirobifluorene, indenofuorene, phenanthrene, thiophene, pyrrole, carbazole, binaphthalene, dehydrophenanthrene, or a combination thereof.

The unit having the hole-transport property may correspond to the hole-transport material HTM in OLED. Suitable organic HTM materials may optionally comprise compounds having the following structural units: phthlocyanine, porphyrine, amine, aryl amine, triarylamine, thiophene, fused thiophene such as dithienothiophene and dibenzothiphene, pyrrole, aniline, carbazole, indolocarbazole, and their derivatives, or a combination thereof.

Examples of cyclic aryl amine-derived compounds that may be used as HTM include, but not limited to, the general structure as follows:
<CHM>
wherein each Ar<NUM> to Ar<NUM> may be independently selected from: cyclic aryl groups such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; and heterocyclic aryl groups such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole, benzimidazole, indoxazine, bisbenzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; groups comprising <NUM> to <NUM> ring structures which may be the same or different types of cyclic aryl or heterocyclic aryl and are bonded to each other directly or through at least one of the following groups, for example: oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structure unit, and aliphatic cyclic group; and wherein each Ar may be further optionally substituted, and the substituents may optionally be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In one aspect, Ar<NUM>to Ar<NUM>may be independently selected from the group consisting of:
<CHM>
<CHM>
<CHM>
wherein n is an integer of <NUM> to <NUM>; X<NUM> to X<NUM>are CH or N; Ar<NUM> is as defined above. Additional non-limiting examples of cyclic aryl amine-derived compounds may be found in <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>.

Suitable non-limiting examples of HTM compounds are set forth in the following table:
<CHM>
<CHM>
<CHM>.

The HTM described above may be incorporated into the polymer of the present disclosure by a hole-transport structural unit.

In some embodiments, the polymers of the present disclosure have electron-transport properties.

In a preferred embodiment, according to one aspect of the present disclosure, wherein Ar2 may be selected from units having electron-transport properties, and preferred electron-transport units may be any one selected from the group consisting of pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole, benzimidazole, indoxazine, bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, or a combination thereof.

The unit having the electron-transport characteristics may correspond to the electron-transport material ETM in the OLED. ETM is also sometimes called n-type organic semiconductor material. In principle, examples of suitable ETM materials are not particularly limited and any metal complexes or organic compounds may be used as ETM as long as they have electron-transport properties. Preferred organic ETM materials may be selected from the group consisting of tris (<NUM>-quinolinolato) aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spiro-bifluorene, phenylene-vinylene, triazine, triazole, imidazole, pyrene, perylene, trans-indenofluorene, cis-indenonfluorene, dibenzol-indenofluorene, indenonaphthalene, benzanthracene and their derivatives, or any combination thereof.

In another aspect, compounds that may be used as ETM may be molecules comprising at least one of the following groups:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
wherein R<NUM> may be selected from the group consisting of: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, wherein, when they are aryl or heteroaryl, they may have the same meaning as Ar<NUM> in HTM as described above; Ar<NUM> - Ar<NUM> may have the same meaning as Ar<NUM> in HTM as described above; n is an integer from <NUM> to <NUM>; and X<NUM> - X<NUM> may be selected from CR<NUM> or N.

Non-limiting examples of suitable ETM compounds are listed in the following
<CHM>.

The ETM described above may be incorporated into the polymer of the present disclosure by an electron-transport structural unit.

The conjugated polymer containing an ethynyl crosslinking group of structural Chemical Formula <NUM> according to one aspect of the present disclosure is provided, wherein R3 is a linking group. In a preferred embodiment, R3 may be selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl having from <NUM> to <NUM> carbon atoms.

In some embodiments, R3 is a non-conjugated linking group, preferably any one selected from the group consisting of alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, or a combination thereof.

In some preferred embodiments, R3 is a conjugated linking group, preferably selected from C1 to C30 alkyl, C1 to C30 alkoxy, benzene, biphenyl, triphenyl, benzo, thiophene, anthracene, naphthalene, benzodithiophene, aryl amine, triphenylamine, naphthylamine, thiophene, carbazole, dibenzothiophene, dithienocyclopentadiene, dithienosilole, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, furan and the like, or a combination thereof.

Non-limiting examples of a suitable linking group R3 with a crosslinkable group are listed in the following table:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

In a preferred embodiment, the conjugated polymer of the present disclosure may have the general formula below:
<CHM>
where x, y and z are mol% which are greater than <NUM> and x + y + z = <NUM>, and Ar2-<NUM> has the same meaning as Ar2 described above.

In a more preferred embodiment, the conjugated polymer as described above is provided, wherein at least one of Ar1, Ar2 and Ar2-<NUM> is selected as a hole-transport unit and at least one selected as an electron-transport unit.

Some of the more preferred combinations of non-limiting examples are:.

In some preferred embodiments, the crosslinking group may be present in an amount of not greater than <NUM> mol%, more preferably not greater than <NUM> mol%, more preferably not greater than <NUM> mol%, and most preferably not greater than 20mol%.

Some non-limiting examples of repeating units containing crosslinking groups are:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

A general synthetic process of a conjugated polymer containing the ethynyl crosslinking group may be: first synthesizing a monomer with a functionalized ethynyl crosslinking group, and then producing the conjugated polymer containing the ethynyl crosslinking group using polymerization processes such as transition metal catalyzed coupling (Suzuki Polymerization, Heck Polymerization, Sonogashira Polymerization, Still Polymerization) and the Witting Reaction. The reaction duration, reaction temperature, monomer ratio, reaction pressure, solubility, amount of catalyst, ligand ratio, phase transfer catalyst, and other parameters may be manipulated to control the molecular weight and dispersion coefficient of the polymer. The synthesis route may be as follows:
<CHM>.

A general synthetic process of a multi- (ternary or above) conjugated polymer containing ethynyl crosslinking group may be: first synthesizing a monomer with a functionalized ethynyl crosslinking group, and then producing the conjugated polymer containing the ethynyl crosslinking group with multiple species f monomers (three kinds or above) using polymerization processes such as transition metal catalyzed coupling (Suzuki Polymerization, Heck Polymerization, Sonogashira Polymerization, Still Polymerization) and the Witting Reaction. The reaction duration, reaction temperature, monomer ratio, reaction pressure, solubility, amount of catalyst, ligand ratio, phase transfer catalyst, and other parameters may be manipulated to control the molecular weight and dispersion coefficient of the polymer. The synthesis route may be as follows:
<CHM>.

For some special polymer reaction, the ethynyl crosslinking group is sensitive to some of the specific chemical reagents, temperature and so on used in the polymer reaction process, which may initiate reaction of the ethynyl group. For example, if the temperature required for the polymerization reaction exceeds <NUM> or even higher than <NUM>, or <NUM>, the cross-linking groups of the conjugated polymer side chains are relatively active at high temperature and result in polymerization reaction of the ethynyl crosslinking groups to each other, generating an insoluble and infusible polymer with no solution processing characteristics. Therefore, under the special polymerization conditions, the terminal hydrogen atoms on the ethynyl crosslinking group may be first protected to reduce its chemical reactivity. The most common protecting group for the terminal hydrogen atom of the ethynyl crosslinking group may be trimethylsilyl (TMS). After formation of a trimeryl-containing polymer precursor, the polymer precursor may be treated with an alkali solution for some time to generate the targeted conjugated polymer, i.e., the conjugated polymer containing the ethynyl crosslinking group. The optimized conjugated polymer synthesis route is shown in the following figure:
<CHM>.

The synthetic route of the conjugated organic monomer containing an ethynyl crosslinking group may be as shown below, but is not limited to the use of the following route to synthesize the target compound. The starting material A (commercial chemical reagents or synthesized via chemical processes) may be obtained by electrophilic optional substitutiion reaction (e.g., halogenation such as chlorination, bromination, iodination) to obtain compound B. And the compound B can react with trimethylsilyl acetylene in a Sonogashira coupling reaction catalyzed by Pd-Cu co-catalyst to yield compound C. The trimethylsilyl protective functional group may be removed from the compound C in an alkaline solution to produce the target compound D.

In order to facilitate understanding of the conjugated polymer containing an ethynyl crosslinking group according to the present disclosure, examples of the conjugated polymers containing an ethynyl crosslinking group are given below, but are not limited thereto. The conjugated polymers containing the ethynyl crosslinking group listed herein have a distinct feature that the ethynyl group is linked to the backbone of the conjugated polymer directly or linked by a chain of conjugated aryl ring or heterocyclic aryl ring. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

The present disclosure also provides a mixture which may comprise a polymer according to one aspect of the disclosure, and at least another organic functional material. The organic functional material may include hole (also referred to as electron hole) injecting 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), multiplet emitter (phosphorescent emitter), especially light-emitting organometallic complexes. Non-limiting examples of various organic functional materials are described, for example, in <CIT>, <CIT>, and <CIT>. The organic functional material may be a small-molecule polymeric material. The following is a more detailed description the organic functional material (but not limited thereto).

HTM has been described earlier and will be further discussed below.

Suitable organic HIM/HTM materials for use in one aspect of the present disclosure may include any one of the compounds having the following structural units: phthalocyanines, porphyrins, amines, aryl amines, biphenyl triaryl amines, thiophenes, thiophenes such as dithiophenethiophene and thiophthene, pyrrole, aniline, carbazole, indeno-fluorene, and derivatives thereof. Other suitable HIMs also include: fluorocarbon-containing polymers; polymers comprising conductive dopants; conductive polymers such as PEDOT/PSS; self-assembled monomers such as compounds comprising phosphonic acid and sliane derivatives; metal oxides, such as MoOx; metal complex, and a crosslinking compound, or a combination thereof.

Other examples of metal complexes that may be used as HTM or HIM may include, but are not limited to, the general structure as follows:
<CHM>
M may be metal having an atomic weight greater than <NUM>;
(Y<NUM>-Y<NUM>) is a bidentate ligand, wherein Y<NUM> and Y<NUM> are independently selected from C, N, O, P, and S; L is an auxiliary ligand; m is an integer from <NUM> to the maximum coordination number of the metal; m + n is the maximum coordination number of the metal.

In one embodiment, (Y<NUM>-Y<NUM>) may be a <NUM>-phenylpyridine derivative.

In another embodiment, (Y<NUM>-Y<NUM>) may be a carbene ligand.

In another embodiment, M may be selected from Ir, Pt, Os, and Zn.

In another aspect, the HOMO of the metal complex is greater than -<NUM> eV (relative to the vacuum level).

ETM has been described earlier and will be further discussed below.

Examples of EIM/ETM material used in one aspect of the present disclosure are not particularly limited, and any metal complex or organic compound may be used as EIM/ETM as long as they can transfer electrons. Preferred organic EIM/ETM materials may be selected from the group consisting of tris (<NUM>-quinolinolato) aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spiro-bifluorene, phenylene-vinylene, triazine, triazole, imidazole, pyrene, perylene, trans-indenofluorene, cis-indenonfluorene, dibenzol-indenofluorene, indenonaphthalene, benzanthracene and their derivatives, or any combination thereof.

The hole-blocking layer (HBL) used in one aspect of the present disclosure is typically used to block holes from adjacent functional layers, particularly light-emitting layers. In contrast to a light-emitting device without a barrier layer, the presence of HBL usually leads to an increase in luminous efficiency. The hole-blocking material (HBM) of the hole-blocking layer (HBL) requires a lower HOMO than the adjacent functional layer, such as the light-emitting layer. In a preferred embodiment, the HBM has a greater energy level of excited state than the adjacent light-emitting layer, such as a singlet or triplet, depending on the emitter. In another preferred embodiment, the HBM has an electron-transport function. Typically, EIM/ETM materials with deep HOMO levels may be used as HBM.

On the other hand, examples of metal complexes that may be used as EIM/ETM may include, but are not limited to, the following general structure:
<CHM>
(O-N) or (N-N) is a bidentate ligand, wherein the metal coordinates with O, N, or N, N; L is an auxiliary ligand; and m is an integer whose value is from <NUM> to the maximum coordination number of the metal.

In another preferred embodiment, the organic alkali metal compound may be used as the EIM. In the present disclosure, the organic alkali metal compound may be understood as a compound having at least one alkali metal, i.e., lithium, sodium, potassium, rubidium, and cesium, and further comprising at least one organic ligand.

Non-limiting examples of suitable organic alkali metal compounds used in one aspect of the present disclosure may include the compounds described in <CIT>, <CIT> and <CIT>.

The preferred organic alkali metal compound may be a compound of the following formula:
<CHM>
wherein R<NUM> has the same meaning as described above, and the arc represents two or three atoms and the bond to form a <NUM>- or <NUM>-membered ring with metal M when necessary, while the atoms may be optionally substituted with one or more R<NUM>; and wherein M is an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium.

The organic alkali metal compound may be in the form of a monomer, as described above, or in the form of an aggregate, for example, two alkali metal ions with two ligands, <NUM> alkali metal ions and <NUM> ligands, <NUM> alkali metal ions and <NUM> ligand, or in other forms.

The preferred organic alkali metal compound may be a compound of the following formula:
<CHM>
wherein, the symbols used are as defined above, and in addition:.

In a preferred embodiment, the alkali metal M is selected from the group consisting of lithium, sodium, potassium, more preferably lithium or sodium, and most preferably lithium.

In a preferred embodiment, the organic alkali metal compound is used in the electron-injection layer, and more preferably the electron-injection layer consists of the organic alkali metal compound.

In another preferred embodiment, the organic alkali metal compound is doped into other ETMs to form an electron-transport layer or an electron-injection layer, more preferably an electron-transport layer.

Non-limiting examples of a suitable organic alkali metal compound are listed in the following table:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

Examples of a triplet host material used in one aspect of the present disclosure are not particularly limited and any metal complex or organic compound may be used as the host material as long as its triplet energy is greater than that of the light emitter, especially a triplet emitter or phosphorescent emitter.

Examples of metal complexes that may be used as triplet hosts may include, but are not limited to, the general structure as follows:
<CHM>
wherein M may be a metal; (Y<NUM>-Y<NUM>) may be a bidentate ligand, Y<NUM> and Y<NUM> may be independently selected from C, N, O, P, and S; L may be an auxiliary ligand; m may be an integer with the value from <NUM> to the maximum coordination number of the metal; and, m + n is the maximum number of coordination of the metal.

In a preferred embodiment, the metal complex which may be used as the triplet host has the following form:
<CHM>
(O-N) may be a bidentate ligand in which the metal is coordinated to O and N atoms.

In one embodiment, M may be selected from Ir and Pt.

Non-limiting examples of organic compounds that may be used as triplet host are selected from: compounds containing cyclic aryl groups, such as benzene, biphenyl, triphenyl, benzo, and fluorene; compounds containing heterocyclic aryl groups, such as triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, indolopyridine, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole, benzimidazole, indoxazine, bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, or a combination thereof; and groups containing <NUM> to <NUM> ring structures, which may be the same or different types of cyclic aryl or heterocyclic aryl and are linked to each other directly or by at least one of the following groups, such as oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structure unit, and aliphatic ring, wherein each Ar may be further optionally substituted and the substituents may be any one of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, or a combination thereof.

In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:
<CHM>
<CHM>
<CHM>
<CHM>.

R<NUM> - R<NUM> may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, which may have the same meaning as Ar<NUM> and Ar<NUM> described above when they are aryl or heteroaryl; n may be an integer from <NUM> to <NUM>; X<NUM> - X<NUM> may be selected from CH or N; and X<NUM> may be selected from CR<NUM>R<NUM> or NR<NUM>.

Non-limiting examples of suitable triplet host material are listed in the following table:
<CHM>
<CHM>.

Examples of singlet host material used in one aspect of the present disclosure are not particularly limited and any organic compound may be used as the host as long as its singlet state energy is greater than that of the light emitter, especially the singlet emitter or fluorescent light emitter.

Non-limiting examples of organic compounds used as singlet host materials may be selected from: cyclic aryl compounds, such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; heterocyclic aryl compounds, such as triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophen, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, indolopyridine, pyrrolodipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazin, oxadiazine, indole, benzimidazole, indoxazine, bisbenzoxazole, isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and groups comprising <NUM> to <NUM> ring structures, which may be the same or different types of cyclic aryl or heterocyclic aryl and are linked to each other directly or by at least one of the following groups, such as oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structure unit, and aliphatic rings.

In a preferred embodiment, the monomorphic host material may be selected from compounds comprising at least one of the following groups:
<CHM>
<CHM>
<CHM>
<CHM>.

R<NUM> may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl; Ar<NUM> is aryl or heteroaryl and has the same meaning as Ar<NUM> defined in the HTM above; n is an integer from <NUM> to <NUM>; X<NUM> - X<NUM> is selected from CH or N; X<NUM> and X<NUM> are selected from CR<NUM>R<NUM> or NR<NUM>.

Non-limiting examples of a suitable singlet host material are listed in the following table:
<CHM>
<CHM>.

The hole-blocking layer (HBL) used in one aspect of the present disclosure is typically used to block holes from adjacent functional layers, particularly light-emitting layers. In contrast to a light-emitting device without a barrier layer, the presence of HBL usually leads to an increase in luminous efficiency. The hole-blocking material (HBM) of the hole-blocking layer (HBL) requires a lower HOMO than the adjacent functional layer, such as the light-emitting layer. In a preferred embodiment, the HBM has a greater energy level of excited state than the adjacent light-emitting layer, such as a singlet or triplet, depending on the emitter. In another preferred embodiment, the HBM has an electron-transport function.

In one embodiment, the HBM used comprises the same molecules as the host material in the light-emitting layer.

In another preferred embodiment, the HBM may be selected from compounds comprising at least one of the following groups:
<CHM>
<CHM>
<CHM>
wherein n may be an integer from <NUM> to <NUM>; L may be an auxiliary ligand; and m may be an integer from <NUM> to <NUM>.

The singlet emitter used in one aspect of the present disclosure tends to have a longer conjugate π-electron system. To date, there have been many examples, such as, but not limited to, any one of styrylamine and its derivatives or combinations thereof, and any one of indenofluorene and its derivatives or combinations thereof.

In a preferred embodiment, the singlet emitter may be selected from the group consisting of monostyry lamines, distyry lamines, tristyrylamines, tetrastyrylamines, styrylphosphines, styryl ethers, and arylamines, or combinations thereof.

Mono styrylamine refers to a compound which comprises an unsubstituted or optionally substituted styryl group and at least one amine, most preferably an aryl amine. Distyrylamine refers to a compound comprising two unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aryl amine. Ternarystyrylamine refers to a compound which comprises three unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aryl amine. Quaternarystyrylamine refers to a compound comprising four unsubstituted or optionally substituted styryl groups and at least one amine, most preferably an aryl amine. Preferred styrene is stilbene, which may be further optionally substituted. The corresponding phosphines and ethers are defined similarly to amines. Aryl amine or aromatic amine refers to a compound comprising three unsubstituted or optionally substituted cyclic or heterocyclic aryl systems directly attached to nitrogen. At least one of these cyclic or heterocyclic aryl systems is preferably selected from fused ring systems and most preferably has at least <NUM> aryl ring atoms. Among the preferred examples are aryl anthramine, aryl anthradiamine, aryl pyrene amines, aryl pyrene diamines, aryl chrysene amines and aryl chrysene diamine. Aryl anthramine refers to a compound in which a diarylamino group is directly attached to anthracene, most preferably at position <NUM>. Aryl anthradiamine refers to a compound in which two diarylamino groups are directly attached to anthracene, most preferably at positions <NUM>, <NUM>. Aryl pyrene amines, aryl pyrene diamines, aryl chrysene amines and aryl chrysene diamine are similarly defined, wherein the diarylarylamino group is most preferably attached to position <NUM> or <NUM> and <NUM> of pyrene.

Non-limiting examples of singlet emitter based on vinylamine and arylamine are also preferred examples which may be found in the following patent documents: <CIT>, <CIT>, <CIT>, <CIT> , <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>.

Non-limiting examples of singlet light emitters based on distyrylbenzene and its derivatives may be found in, for example, <CIT>.

Further preferred singlet emitters may be selected from the group consisting of: indenofluorene-amine, indenofluorene-diamine, benzoindenofluorene-amine, benzoindenofluorene-diamine, dibenzoindenofluorene-amine, and dibenzoindenofluorene-diamine.

Other materials useful as singlet emissors include, but are not limited to, polycyclic aryl compounds, especially any one selected from the derivatives of the following compounds: anthracenes such as <NUM>,<NUM>-di -naphthylanthracene, naphthalene, tetraphenyl, phenanthrene, perylene such as <NUM>,<NUM>,<NUM>,<NUM>-tetra-t-butylatedylene, indenoperylene, phenylenes such as <NUM>,<NUM> '-(bis (<NUM>-ethyl-<NUM>-carbazovinylene) -<NUM>,<NUM>'-biphenyl, periflanthene, decacyclene, coronene, fluorene, spirobifluorene, arylpyren (e.g., <CIT>), arylenevinylene (e.g., <CIT>, <CIT>), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarine, rhodamine, quinacridone, pyrane such as <NUM> (dicyanoethylene) -<NUM>-(<NUM>-dimethylaminostyryl-<NUM>-methyl) -<NUM>-pyrane (DCM), thiapyran, bis (azinyl) imine-boron compounds (<CIT>), bis (azinyl) methene compounds, carbostyryl compounds, oxazone, benzoxazole, benzothiazole, benzimidazole, and diketopyrrolopyrrole, or combinations thereof. Non-limiting examples of some singlet emitter material may be found in the following patent documents: <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>.

Non-limiting examples of suitable singlet emitters are listed in the following table:
<IMG>.

The triplet emitter used in one aspect of the present disclosure is also called a phosphorescent emitter. In a preferred embodiment, the triplet emitter may be a metal complex of the general formula M (L) n, wherein M may be a metal atom; L may be a same or different ligand each time it is present, and may be bonded or coordinated to the metal atom M at one or more positions; n may be an integer greater than <NUM>, preferably <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM>. Alternatively, these metal complexes may be attached to a polymer by one or more positions, most preferably through an organic ligand.

In a preferred embodiment, the metal atom M may be selected from the group consisting of transition metal elements or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, and particularly preferably Os, Ir, Ru, Rh, Re, Pd, or Pt.

Preferably, the triplet emitter comprises a chelating ligand, i.e., a ligand, coordinated to the metal by at least two bonding sites, and it is particularly preferred that the triplet emitter comprises two or three identical or different bidentate or multidentate ligand. Chelating ligands help to improve stability of metal complexes.

Non-limiting examples of organic ligands may be selected from the group consisting of phenylpyridine derivatives, <NUM>,<NUM>-benzoquinoline derivatives, <NUM> (<NUM> -thienyl) pyridine derivatives, <NUM> (<NUM>-naphthyl) pyridine derivatives, or <NUM> phenylquinoline derivatives. All of these organic ligands may be optionally substituted, for example, optionally substituted with fluoromethyl or trifluoromethyl. The auxiliary ligand may be preferably selected from acetylacetonate or picric acid.

In a preferred embodiment, the metal complex which may be used as the triplet emitter may have the following form:
<CHM>.

Non-limiting examples of triplet emitter materials that are extremely useful may be found in the following patent documents and references: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <NPL>, <CIT>, <CIT>, <NPL>, <NPL>, <NPL>, <CIT>, <NPL>, <NPL>, <NPL>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>.

Non-limiting examples of suitable triplet emitter are given in the following table:
<IMG>.

In some embodiments, the organic functional materials described above, including HIM, HTM, ETM, EIM, Host, fluorescent emitter, and phosphorescent emitters, may be in the form of polymers.

In a preferred embodiment, the polymer suitable for the present disclosure is a conjugated polymer. In general, the conjugated polymer may have the general formula:
<CHM>
wherein B, A may
be independently selected as the same or different structural elements in multiple occurrences.

B: a π-conjugated structural unit with relatively large energy gap, also referred to as backbone unit, which may be selected from monocyclic or polycyclic aryl or heteroaryl, preferably in the form of benzene, biphenylene, naphthalene, anthracene, phenanthrene, dihydrophenanthrene, <NUM>,<NUM>-dihydrophenanthroline, fluorene, difluorene, spirobifluorene, p-phenylenevinylene, trans-indenofluorene, cis-indenofluorene, dibenzol-indenofluorene, indenonaphthalene and derivatives thereof, or a combination thereof.

A: a π-conjugated structural unit with relatively small energy gap, also referred to as a functional unit, which, according to different functional requirements, may be selected from the above-mentioned hole-injection or hole-transport material (HIM/HTM), hole-blocking material (HBM), electron-injection or electron-transport material (EIM/ETM), electron-blocking material (EBM), organic host material (Host), singlet emitter (fluorescent emitter), multiplet emitter (phosphorescent emitter), or a combination thereof.

Non-limiting examples of light-emitting polymers are disclosed in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>.

In another embodiment, the polymers suitable for the present disclosure may be non-conjugated polymers. The nonconjugated polymer may be the backbone with all functional groups on the side chain. Non-limiting examples of such nonconjugated polymers for use as phosphorescent host or phosphorescent emitter materials may be found in patent applications such as <CIT>, <CIT>, <CIT> and <CIT>. Non-limiting examples of such nonconjugated polymers used as fluorescent light-emitting materials may be found in the patent applications <CIT>, <CIT>, and <CIT>. In addition, the non-conjugated polymer may also be a polymer, with the conjugated functional units on the backbone linked by non-conjugated linking units. Non-limiting examples of such polymers are disclosed in <CIT> and <CIT>.

The present disclosure also provides a formulation which may comprise a conjugated organic polymer as described in one aspect of the present disclosure and at least one organic solvent. Examples of the organic solvents include, but are not limited to, methanol, ethanol, <NUM>-methoxyethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, <NUM>,<NUM>-dioxahexane, acetone, methyl ethyl ketone, <NUM>,<NUM>-dichloroethane, <NUM>-phenoxytoluene, <NUM>,<NUM>,<NUM> - trichloroethane, <NUM>,<NUM>,<NUM>,<NUM>-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, naphthane, indene and/or their formulations.

In a preferred embodiment, the formulation according to one aspect of the disclosure is a solution.

In another preferred embodiment, the formulation according to one aspect of the disclosure is a suspension.

The formulation in the examples of the present disclosure may comprise an organic mixture from <NUM> to <NUM> wt%, more preferably from <NUM> to <NUM> wt%, more preferably from <NUM> to <NUM> wt%, and most preferably from <NUM> to <NUM> wt%.

The present disclosure also provides the use of said formulation as a coating or printing ink in the preparation of organic electronic devices, and particularly preferaby by means of printing or coating in a preparation process.

Among them, suitable printing or coating techniques may include, but are not limited to, ink-jet printing, typography, screen printing, dip coating, spin coating, blade coating, roll printing, torsion printing, lithography, flexography, rotary printing, spray coating, brush coating or pad printing, slit type extrusion coating, and so on. Preferred are inkjet printing, screen printing and gravure printing. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders, etc., for adjusting viscosity, film forming properties, improving adhesion, and the like. For more information about printing techniques and their requirements for solutions, such as solvent, concentration, viscosity, etc., see <NPL>.

Based on the above polymers, the present disclosure also provides use of the polymers as described above, i.e. application of the polymers to an organic electronic device, which may be selected from, but not limited to, organic light emitting diodes (OLED), organic photovoltaics (OPVs), organic light emitting cells (OLEEC), organic field effect transistor (OFET), organic light emitting field effectors, organic lasers, organic spin electron devices, organic sensors, and organic plasmon emitting diodes, especially OLED. In a particularly preferred embodiment, the polymer according to one aspect of the present disclosure is used in an electrion-transport layer, especially a hole-transport layer, of an organic electronic device.

The present disclosure further provides an organic electronic device which may comprise at least one polymer as described above. Typically, such an organic electronic device may comprise at least a cathode, an anode, and a functional layer between the cathode and the anode, wherein the functional layer may comprise at least one of the polymers as described above.

In a preferred embodiment, the above-described organic electronic device is an electroluminescent device, which may include a substrate, an anode, at least one light-emitting layer, and a cathode. In a particularly preferred embodiment, the organic electronic device described above may be an OLED.

The substrate may be opaque or transparent. Transparent substrates may be used to make transparent light-emitting components. See, for example, <NPL>, and <NPL>. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Most preferably the substrate has a smooth surface. Substrates free of surface defects are particularly desirable. In a preferred embodiment, the substrate is flexible and may be selected from polymer films or plastic, with a glass transition temperature (Tg) of <NUM> or above, more preferably above <NUM>, more preferably above <NUM>, and most preferably above <NUM>. Non-limiting examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (<NUM>,<NUM>-naphthalene) (PEN).

The anode may comprise a conductive metal or a metal oxide, or a conductive polymer. The anode may easily inject holes into the hole-injection layer (HIL) or the hole-transport layer (HTL) or the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or the valence band energy level of the emitter in the light-emitting layer or of the p-type semiconductor material of the HIL or HTL or the electron-blocking layer (EBL) may be smaller than <NUM> eV, more preferably smaller than <NUM> eV, and most preferably smaller than <NUM> eV. Non-limiting examples of anode materials may 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 may be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as suitable physical vapor deposition, including RF magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In some embodiments, the anode may be patterned. The patterned ITO conductive substrate is commercially available and may be used to fabricate the device according to the disclosure.

The cathode may comprise a conductive metal or a metal oxide. The cathode may easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or the valence band energy level of the emitter in the light-emitting layer or of the n-type semiconductor material of the electron-injection layer (EIL) or the electron-transport layer (ETL) or the hole-blocking layer (HBL) may be smaller than <NUM> eV, more preferably smaller than <NUM> eV, and most preferably smaller than <NUM> eV. In principle, all of the material that may be used as the cathode of an OLED may serve as a cathode material for the device of the present disclosure. Examples of the cathode material may include, but are not limited to, any one of Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloys, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, or a combination thereof. The cathode material may be deposited using any suitable technique, such as suitable physical vapor deposition, including RF magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

OLEDs may also comprise 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), and hole-blocking layer (HBL), or a combination thereof. Materials suitable for use in these functional layers are described in detail in <CIT>, <CIT>, and <CIT>.

In a preferred embodiment, in the light emitting device according to one aspect of the present disclosure, the light-emitting layer thereof may be prepared by printing with the formulation of the present disclosure.

The light emitting device according to one aspect of the present disclosure may have a light emission wavelength between <NUM> and <NUM>, more preferably between <NUM> and <NUM>, and more preferably between <NUM> and <NUM>.

The disclosure also provides the use of organic electronic devices according to one aspect of the disclosure in a variety of electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

The disclosure also provides an electronic device comprising an organic electronic device as described in an aspect of the disclosure, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

The disclosure will now be described with reference to the preferred embodiments, but the disclosure is not to be construed as being limited to the following examples. It is to be understood that the appended claims are intended to cover the scope of the disclosure. Those skilled in the art will understand that modifications can be made to various embodiments of the disclosure with the teaching of the present disclosure, which will be covered by the spirit and scope of the claims of the disclosure.

To a <NUM> three-necked round bottom flask, <NUM> (<NUM> mol) of <NUM>,<NUM>-dibromo-p-xylene and <NUM> (<NUM> mmol) of phenylboronic acid was added. <NUM> of toluene was added and stirred to dissolve, followed by <NUM> water and <NUM> Na<NUM>CO<NUM> (<NUM> mol), stirring all solids were dissolved. <NUM> of Aliquat <NUM> and <NUM> of tetra(triphenylphosphine) palladium catalyst (<NUM>) ((PPh<NUM>)<NUM>Pd) were added and flushed with protective nitrogen gas for <NUM> before heated to reflux (<NUM>-<NUM>). After refluxing for <NUM>, the nitrogen gas was turned off and the system kept sealed, reflexing and reacting overnight. The reaction solution was extracted with toluene (<NUM> x <NUM>) after cooling, and the organic phase was combined and successively washed with saturated solution of NaCl and water. White crystal <NUM> was obtained by evaporation of the solvent and drying, with the theoretical value of <NUM> and a yield rate of about <NUM>%. <NUM>-<NUM> (lit. <NUM>), <NUM>H NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM>-<NUM> (m, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>).

To a <NUM> three-necked round bottom flask, <NUM> (<NUM> mol) of <NUM>,<NUM>-diphenyl-p-xylene and <NUM> of pyridine was added under mechanical stirring to dissolve, followed by <NUM> of water and <NUM> of KMnO<NUM> (<NUM> mol). It was heated to reflux (about <NUM>-<NUM>) for <NUM>, during which it was cooled after every <NUM> of refluxing and added with <NUM> of water and <NUM> of KMnO<NUM> (<NUM> mol), repeated for four times in total. Afterwards, it was cooled after every <NUM> of refluxing and added with <NUM> of water, repeated for four times in total. After the reaction, filtration was done when hot. The filter cake was rinsed with boiling water (<NUM> x <NUM>), the filtrate was combined, and the solvent was evaporated to about <NUM>, to which <NUM> of concentrated hydrochloric acid was added. After cooling, filtration, and washing with cold water, it was dried in vacuo to give <NUM> of white solid, with the theoretical value of <NUM> and a yield rate of about <NUM>%. <NUM>-<NUM> (lit. <NUM>), <NUM>H NMR (DMSO-d<NUM>, <NUM>, ppm): δ <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>).

To a <NUM> three-necked round bottom flask, <NUM> of concentrated sulfuric acid was added, followed by slow addition of <NUM> of <NUM>,<NUM>-diphenylcarbodiimide (<NUM> mol) under stirring. Reaction was allowed under room temperature for <NUM> and followed by the addition of <NUM>-<NUM> drops of fuming sulfuric acid. After <NUM> of reaction, the reaction solution was poured into ice-water mixture and stirred with a glass rod. The mixture was filtered by suction, rinsed with a large amount of water, and dried to give a dark red solid of <NUM>, with the theoretical value of <NUM> and a yield rate of about <NUM>%. ><NUM> (lit. ><NUM>), <NUM>H NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>).

To a <NUM> three-necked round bottom flask, <NUM> of <NUM>,<NUM>-indolifluinedione (<NUM> mol) was added, and then slowly <NUM> of diethylene glycol and <NUM> of hydrazine hydrate (<NUM>%) successively added with stirring, followed by <NUM> of KOH(<NUM> mol) ground into fine powder. After flushing with protective nitrogen gas for <NUM>, it was heated to reflux (<NUM>) for reaction of <NUM>, before the mixture was cooled and poured into a mixed solution of crushed ice/concentrated hydrochloric acid (v: v = <NUM>: <NUM>) , while stirring with a glass rod. The mixture was filtered by suction, washed with water, and dried to obtain a yellowish gray solid of <NUM>, with the theoretical value of <NUM> and a yield rate of <NUM>%. <NUM>-<NUM> (lit. <NUM>-<NUM>), <NUM>H NMR (DMSO-d<NUM>, <NUM>, ppm): δ <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (s, <NUM>).

To a <NUM> three-necked round bottom flask, a stir bar and <NUM> of indenofuorene (<NUM>) were added, and a high vacuum piston (paraffin seal) was placed in the middle while rubber stoppers were place on both sides. The flask was heated with a blower while being evacuated with an oil pump. <NUM> of dry THF was added to the flask with a syringe. <NUM> of <NUM> n-butyllithium (<NUM> mmol) was added dropwise to the flask using a syringe under stirring at -<NUM> and reacted under nitrogen protection for <NUM>. The system was allowed to warm up to room temperature for <NUM> of reaction and then cooled to -<NUM>. <NUM> of <NUM>-bromooctane (n-C<NUM>H<NUM>Br,<NUM> mmol) was added with a syringe, reacted at room temperature for <NUM> at -<NUM>, spontaneously warmed up to room temperature, and reacted overnight. The reaction was quenched by the addition of about <NUM> of water. The reaction solution was extracted with petroleum ether (<NUM> x <NUM>). The organic phase was combined and dried over anhydrous Na<NUM>SO<NUM>. The solvent was evaporated before purification by column chromatography (<NUM>-<NUM> mesh silica gel/petroleum ether). Recrystallization from methanol gave <NUM> of beige crystals, with the theoretical value of <NUM> and a yield rate of about <NUM>%. <NUM>H NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>); <NUM>C NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

To a <NUM> three-necked round bottom flask, a stir bar, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetraoctylindenofuorene (<NUM> mmol), and <NUM> of CCl4 were added, dissolved by stirring. <NUM> Al<NUM>O<NUM>/CuBr (<NUM> mol) was added for reaction under refluxing for <NUM>. The reaction mixture was filtered and the filtrate was washed with water and dried over anhydrous Na<NUM>SO<NUM>. The solvent was evaporated and the resulting solid was recrystallized in methanol to give <NUM> of white crystals with the theoretical value of <NUM> and a yield rate of about <NUM>%. <NUM>H NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>); <NUM>C NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

To a <NUM> three-necked round bottom flask, a stir bar was added, and a high vacuum piston was placed in the middle while rubber stoppers were place on both sides. The flask was heated with a blower while being evacuated with an oil pump. A solution of <NUM> of <NUM>,<NUM>-dibromo-<NUM>,<NUM>,<NUM>,<NUM>-tetraoctylindenofuorene (<NUM> mmol) in <NUM> of THF was added to the flask using a syringe and stirred at -<NUM> for <NUM>. Then, <NUM> of <NUM> n-butyllithium (<NUM> mmol) was added dropwise with a syrange, reacted under protective nitrogen gas for <NUM>. <NUM> of <NUM>-isopropyl-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM> -dioxaborane was added dropwise with a syrange, reacted at -<NUM> for <NUM> and then allowed to warm up to room temperature for reaction overnight. The reaction was quenched by adding <NUM> of water to the flask. The reaction was extracted with ether (<NUM> x <NUM>). The organic phase was combined and dried over anhydrous Na<NUM>SO<NUM>. The solvent was evaporated before purification by column chromatography (<NUM>-<NUM> mesh silica gel/ethyl acetate v: v = <NUM>: <NUM>) to give <NUM> of white crystals, with the theoretical value of <NUM> and the yield rate of about <NUM>%. <NUM>H NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM> (d, J = <NUM>, <NUM>), <NUM> (d, J = <NUM>, <NUM>), <NUM> (s, <NUM>), <NUM> (s, <NUM>) <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (q, J = <NUM>, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (t, J = <NUM>, <NUM>), <NUM> (t, J = <NUM>, <NUM>); <NUM>C NMR (CDCl<NUM>, <NUM>, ppm): δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>.

To a <NUM> three-necked round bottom flask, <NUM> of triphenylamine (<NUM> mol) was added, <NUM> of N, N-dimethylformamide was added slowly with stirring, and <NUM> (<NUM> mol) of N-bromosuccinimide ground into fine power was added in several batches. The reaction was performed under nitrogen protection at room temperature in the dark for <NUM>. After cooling, it was poured into crushed ice and extracted three times with dichloromethane. The organic phases were combined and washed three times with water. <NUM>-<NUM> mesh silica gel column was used for separation, while the eluent was for petroleum ether. The product was <NUM> with a yield rate of <NUM>%.

To a <NUM> three-necked round bottom flask, <NUM>-bromotriphenylamine (<NUM>, <NUM> mmol), CuI (<NUM>, <NUM> mmol), (Ph<NUM>P)<NUM>PdCl<NUM> (<NUM>, <NUM> mmol), <NUM> of degassed toluene, and <NUM> of degassed diisopropylamine were added under stirring to dissolve and mix evenly. A solution of trimethylethynylsilane (<NUM>, <NUM> mmol) in diisopropylamine (<NUM>) was added dropwise under argon at room temperature. After the dropwise addition, the temperature of the reaction solution was raised to <NUM> and the reaction was carried out under argon for <NUM> hours. The reaction progress was monitored by thin layer chromatography. After completion of the reaction, the reaction solution was cooled to room temperature, and the impurities such as solid salt were removed by filtration. The crude product was separated and purified by column chromatography (silica gel column, with eluent as petroleum ether), and further recrystallized from methanol to give a white solid which was filtered and dried in vacuo to give <NUM> of a yield rate of <NUM>%.

To a <NUM> three-necked round bottom flask, <NUM> of <NUM>-trimethylsilylethynyltriphenylamine (<NUM> mol) was added, <NUM> of N, N-dimethylformamide was added slowly with stirring, and <NUM> (<NUM> mol)of N-bromosuccinimide ground into fine power was added in several batches. The reaction was performed under nitrogen protection at room temperature in the dark for <NUM>. After cooling, it was poured into crushed ice and extracted three times with dichloromethane. The organic phases were combined and washed three times with water. <NUM>-<NUM> mesh silica gel column was used for separation, while the eluent was for petroleum ether. The product was <NUM> with a yield rate of <NUM>%.

In a <NUM> two-necked round bottom flask, <NUM> (<NUM> mmol) of monomer <NUM>,<NUM>-dibromo-<NUM>'-trimethylsilyl ethynyltriphenylamine, <NUM> (<NUM> mmol) of monomer <NUM>, <NUM>-bis (<NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>,<NUM>-dioxaborolane-diyl) -<NUM>,<NUM>,<NUM>,<NUM>-tetraoctylindenofuorene, <NUM> of Pd(PPh<NUM>)<NUM>, <NUM> of degassed toluene, <NUM> of degassed tetrahydrofuran, and <NUM> of a <NUM> wt% aqueous solution of tetraethylammonium hydroxide were added, homogenized, and flushed with argon for <NUM> minutes. The reaction was carried out under argon protection at <NUM> for <NUM> hours, followed by the succeisve addition of <NUM>µL of bromobenzene to reflux for <NUM> hours and <NUM> of phenylboronic acid to reflux for <NUM> hours. After the reaction was completed and cooled to room temperature, the reaction solution was added dropwise to methanol for precipitation. The resulting flocculent precipitate was filtered, dried in vacuo, and the resulting polymer was redissolved in about <NUM> of tetrahydrofuran. The resulting tetrahydrofuran solution was filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of <NUM>, distilled under reduced pressure, concentrated, and added dropwise to methanol for precipitation. The precipitate was dried in vacuo to give <NUM> of pale yellow solid with a yield rate of <NUM>%. GPC (tetrahydrofuran, polystyrene standard sample) Mn = <NUM>/mol, PDI = <NUM>.

To a solution of polymer P1 (<NUM>) in tetrahydrofuran (<NUM>), <NUM> of <NUM> wt% potassium hydroxide aqueous solution was added, followed by the addition of <NUM> of methanol to dilute the reaction solution. The reaction was stirred under argon at room temperature for <NUM> hour. After completion of the reaction, the reaction solution was poured into ice water and extracted with trichloromethane. The oil layers were washed with water, saturated sodium chloride aqueous solution and concentrated to obtain a crude product. The crude product was separated and purified by column chromatography (silica gel column, with eluent as petroleum ether) and further recrystallized in methanol to give a white solid, which was filtered and dried in vacuo to give a yield of <NUM> with a yield rate of <NUM>%. GPC (tetrahydrofuran, polystyrene standard sample) Mn = <NUM>/mol, PDI = <NUM>.

The polymer P2 prepared in Example <NUM> was used as a hole-transport material in an organic/polymer electroluminescent device O/PLEDs (ITO anode/hole-transport layer/light-emitting layer/electron-transport layer/aluminum cathode).

Claim 1:
A conjugated polymer containing an ethynyl crosslinking group, characterized by having the following structure:
<CHM>
wherein, x and y are mole percentages which are greater than <NUM> and x + y = <NUM>;
<CHM>
is
<CHM>
and
Ar1 is selected from the group consisting of benzene, thiophene, carbazole, indenofluorene, and indolocarbazole, and Ar1 is optionally substituted with any one group selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, or a combination thereof.