CN114031752B - Polymeric crosslinkable compounds, process for their preparation and their use - Google Patents

Polymeric crosslinkable compounds, process for their preparation and their use Download PDF

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CN114031752B
CN114031752B CN202011602574.8A CN202011602574A CN114031752B CN 114031752 B CN114031752 B CN 114031752B CN 202011602574 A CN202011602574 A CN 202011602574A CN 114031752 B CN114031752 B CN 114031752B
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郑江波
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Guangdong Juhua Printing Display Technology Co Ltd
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Abstract

The invention discloses a polymeric crosslinkable compound, a preparation method thereof and an electron transport material. The polymeric crosslinkable compound has a structure as shown in the general formula (I). The polymer formed after crosslinking is not easy to be dissolved by a conventional solvent, so that the crosslinked functional layer is not easy to be mutually dissolved or mixed with the next functional layer, and the influence on the performance of a device is avoided. Moreover, the polymeric crosslinkable compound has good thermal stability at room temperature, excellent electron transport property and higher triplet state energy level, and can realize crosslinking at high temperature without generating any byproducts, thus having great potential in a dissolvable OLED device.

Description

Polymeric crosslinkable compounds, process for their preparation and their use
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a polymeric crosslinkable compound, a preparation method thereof and an electron transport material.
Background
The solution processing method for preparing the OLED device is a low-cost processing method, can be used for preparing the OLED device in a large area, and can be used for obtaining a large-size OLED display panel, so that the method is interesting for a plurality of manufacturers. The OLED device is formed by stacking a carrier injection layer, a carrier transport layer, and a light emitting layer. On the one hand, if the conventional solution processing method is used, the mixing between the functional layers is likely to be caused, so that the performance of the device is reduced, and how to implement solution processing of multiple functional layers without affecting the performance of the device is a problem to be solved. On the other hand, most of the electron transport layer materials on the market at present are based on vacuum vapor deposition type materials, and there are few electron transport layer materials suitable for solution processing. Thus, there remains a great challenge to develop fully solubilized processed OLED devices.
The design of the solubilized electron transport layer material is divided into two ideas: the small molecular electron transport layer material is a small molecular electron transport layer material, and the structure is subjected to modification design again so that the small molecular electron transport layer material can be subjected to dissolution processing, however, the small molecular electron transport layer material is easily dissolved by a solvent of a next functional layer in the solution processing process, and because the common organic small molecular material has good solubility in a common organic solvent, the solvent used in a later layer is difficult to ensure that the solvent does not dissolve a deposited material of a previous layer, so that the solvent can be selected in a narrow range. The other type is a polymer type electron transport layer material, and the design thought is different from that of a small molecular electron transport layer material, so that the synthesis difficulty is high, and few reports based on the polymer type electron transport layer material are provided at present.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a polymeric crosslinkable compound which can be dissolved in a solvent before crosslinking, but the polymer formed after crosslinking is not easily dissolved by a conventional solvent, so that the crosslinked functional layer is not easily mutually dissolved or mixed with the next functional layer, thereby avoiding affecting the performance of the device. Moreover, the polymeric crosslinkable compound has good thermal stability at room temperature, excellent electron transport property and higher triplet state energy level, and can realize crosslinking at high temperature without generating any byproducts, thus having great potential in a dissolvable OLED device.
The polymeric crosslinkable compound has a structure according to formula (1):
Figure BDA0002869703440000011
wherein:
R 1 independently selected from C1-C25 straight chain alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000012
Ar is selected from aryl with the number of ring atoms of 5-20;
R 3 selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a is an integer from 1 to 2;
b is an integer of 1 to 5;
m and n each represent the number of structural units, m: n=1:99-99:1.
The invention also provides a preparation method of the polymeric crosslinkable compound.
The preparation method of the polymeric crosslinkable compound comprises the following steps:
polymerizing a compound having a structure of formula a, a compound having a structure of formula B, and a compound having a structure of formula C;
Figure BDA0002869703440000021
wherein:
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, C3-C25 ringAlkyl or
Figure BDA0002869703440000022
Ar is selected from aryl with the number of ring atoms of 5-20;
R 3 selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a is an integer from 1 to 2;
b is an integer of 1 to 5;
X 0 represents halogen.
The present invention further relates to an electron transport material comprising the polymeric crosslinkable compound as described above, or comprising the polymeric crosslinkable compound prepared by the above-described preparation method.
The invention further relates to a light emitting diode comprising an electron transport layer, the material of which comprises a polymeric crosslinkable compound as described above, or comprises a polymeric crosslinkable compound prepared by the above preparation method, or comprises an electron transport material as described above.
The beneficial effects are that:
the polymeric crosslinkable compound of the invention consists of a main chain structural unit, an electron transport structural unit and a crosslinkable structural unit. The main chain structural unit is selected from fluorene structural units with stability and solubility, and the electron transmission structural unit is selected from phosphine oxide structural units, so that the structural unit has good electron transmission performance and good heat resistance stability; the crosslinkable structural unit is a derivative based on a benzocyclobutene structure which is stable at room temperature but capable of ring-opening crosslinking at high temperatures. The polymeric crosslinkable compound disclosed by the invention can be dissolved in a solvent before crosslinking, and a polymer formed after crosslinking is not easy to dissolve by a conventional solvent, so that the compound has good solvent resistance. And the compound constructed based on the three structural units has good thermal stability at room temperature, simultaneously keeps excellent electron-withdrawing capability of the phosphine oxide structural units, has good electron transmission performance, has higher triplet state energy level, and can effectively block quenching of excitons. In addition, the compounds have great potential in soluble OLED devices due to the ability to achieve crosslinking at high temperatures without the generation of any by-products.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting diode device.
Detailed Description
The invention provides a polymeric crosslinkable compound, a preparation method thereof and an electron transport material. The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. Containing a plurality of R as shown in the general formula 1 R is then 1 May be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: c (C) 1-30 Alkyl, heterocyclic group having 3 to 20 ring atoms, aryl group having 5 to 20 ring atoms, heteroaryl group having 5 to 20 ring atoms, silyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, -NRR', cyano group, isocyano group, isocyanate group, thiocyanate group, isothiocyanato groupAn acid ester group, a hydroxyl group, a trifluoromethyl group, a nitro group, or a halogen, and the above groups may be further substituted with a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, C 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms or heteroaryl having 5 to 10 ring atoms; the C is 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms, or heteroaryl having 5 to 10 ring atoms is optionally further substituted with one or more of the following groups: c (C) 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, e.g., "C 1-9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentylA group, cyclopentyl group, 1-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group, 4-methyl-2-pentyl group, n-hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, n-heptyl group, 1-methylheptyl group, 2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, tert-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyloctyl group, 3, 7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-octyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, adamantyl and the like.
An aryl group refers to a hydrocarbon group containing at least one aromatic ring. Heteroaryl refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. Fused ring aromatic group means that the ring of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. Fused heterocyclic aromatic groups refer to fused ring aromatic hydrocarbon groups containing at least one heteroatom. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic ring systems but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, and the like are also considered fused ring aromatic ring systems for the purposes of this invention.
In a preferred embodiment, the aromatic group is selected from the group consisting of: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaryl group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primary pyridines, quinazolines, quinazolinones, and derivatives thereof.
"amine group" refers to a derivative of ammonia having the formula-N (X) 2 Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH 2 -N (alkyl) 2 -NH (alkyl), -N (cycloalkyl) 2 -NH (cycloalkyl), -N (heterocyclyl) 2 -NH (heterocyclyl), -N (aryl) 2 -NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
In the present invention "×" associated with a single bond represents a linking or fusing site;
in the present invention, when no linking site is specified in the group, an optionally-ligatable site in the group is represented as a linking site;
in the present invention, when no condensed site is specified in the group, it means that an optionally condensed site in the group is used as a condensed site, and preferably two or more sites in the group at ortho positions are condensed sites;
a polymeric crosslinkable compound having a structure according to formula (I):
Figure BDA0002869703440000041
wherein:
R 1 independently selected from C1-C25 straight chain alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000042
Ar is selected from aryl with the number of ring atoms of 5-20;
R 3 selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a is an integer from 1 to 2;
b is an integer of 1 to 5;
m and n each represent the number of structural units, m: n=1:99-99:1.
It will be appreciated that the ratio of m/n will be different, the molecular structure will be different and the properties will be different. The number of defined building blocks can be calibrated by measuring their molecular weight.
In a preferred embodiment, the polymeric crosslinkable compound has a structure as shown in formula (II):
Figure BDA0002869703440000051
preferably L 1 Selected from single bonds, from substituted or unsubstitutedSubstituted aryl with 5-10 ring atoms. More preferably L 1 Selected from single bond or phenyl.
Preferably L 2 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 2 Selected from single bond or phenyl.
In a preferred embodiment, the polymeric crosslinkable compound has a structure as shown in formula (II-1) or formula (II-2):
Figure BDA0002869703440000052
preferably, ar is selected from an aromatic group having 5 to 10 ring atoms.
More preferably, ar is selected from phenyl. At this time, the polymerizable crosslinkable compound has a structure represented by any one of the general formulae (II-3) to (II-5):
Figure BDA0002869703440000053
Figure BDA0002869703440000061
in some preferred embodiments, R 1 Independently selected from C5-C15 straight chain alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl or
Figure BDA0002869703440000062
Further preferably, R 3 Selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
In some preferred embodiments, R 2 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
The structures of the polymeric crosslinkable compounds described herein include, but are not limited to:
Figure BDA0002869703440000063
Figure BDA0002869703440000071
Figure BDA0002869703440000081
wherein, -C 6 H 13 、-C 8 H 17 、-C 12 H 25 All represent straight chain alkyl groups.
m is 6, n is 1, and it does not indicate that the number of structural units is 6 and 1, but indicates that the number of structural units is 6 parts and 1 part. Similarly, m is 11 and n is 2, and it does not indicate that the number of structural units is 11 and 2, but indicates that the number of structural units is 11 parts and 2 parts.
The preparation method of the polymeric crosslinkable compound comprises the following steps:
polymerizing a compound having a structure of formula a, a compound having a structure of formula B, and a compound having a structure of formula C;
Figure BDA0002869703440000082
wherein:
R 1 independently selected from C1-C25 straight chain alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000083
Ar is selected from aryl with the number of ring atoms of 5-20;
R 3 selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkylOr C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a is an integer from 1 to 2;
b is an integer of 1 to 5;
X 0 represents halogen.
Preferably, the compound having the structure of formula A has a structure as shown in general formula (A-1):
Figure BDA0002869703440000084
preferably, the compound having the structure of formula B has a structure as shown in the general formula (B-1):
Figure BDA0002869703440000091
preferably L 1 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 1 Selected from single bond or phenyl.
Preferably L 2 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 2 Selected from single bond or phenyl.
In a preferred embodiment, the compound having the structure of formula C has a structure as shown in formula (C-1) or (C-2):
Figure BDA0002869703440000092
preferably, ar is selected from an aromatic group having 5 to 10 ring atoms.
More preferably, ar is phenyl. At this time, the compound having the structure of formula A has a structure represented by any one of the formulae (A-2) to (A-4):
Figure BDA0002869703440000093
in some preferred embodiments, R 1 Independently selected from C5-C15 straight chain alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl or
Figure BDA0002869703440000094
Further preferably, R 3 Selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
In some preferred embodiments, R 2 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
An electron transport material comprising the crosslinkable polymer described above, or comprising a crosslinkable polymer produced by the production method described above.
In one embodiment, the electron transport layer is prepared by printing or coating. In one embodiment, the light emitting diode of the present invention is selected from solution type light emitting diodes, and the functional layers thereof are all prepared by printing or coating.
In the light emitting device, especially the OLED, the light emitting device comprises a substrate, an anode, at least one light emitting layer and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer (EML). In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF 2 /Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may 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), a Hole Blocking Layer (HBL).
The invention also relates to the use of the light emitting diode according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The invention also relates to an electronic device comprising a light emitting diode according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor, etc.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In the following examples, the substituents are not explicitly indicated and all represent straight-chain structures, i.e. -C 6 H 13 、-C 8 H 17 、-C 12 H 25 All represent straight chain alkyl groups.
In the following examples, toluene was used as a solvent; palladium acetate is the catalyst; tris (2-methoxyphenyl) phosphine is a catalyst ligand; tetraethylammonium hydroxide is a base and plays a role in promoting the reaction; phenylboronic acid is the last molecule to be used as a polymer end cap, the end cap concept being the reaction of unreacted bromo groups in the polymer with phenylboronic acid, thereby leaving no bromine in the polymer chain. Because the presence of bromine atoms quenches luminescence to some extent.
1. Synthesis of Compounds
Example 1 Compound P1 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000101
3.6mmol of phosphine oxide derivatives->
Figure BDA0002869703440000102
0.6mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000111
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then vacuum-pumping and nitrogen-exchanging operation is implemented, 3 times of repetition are implemented, and then injection is implemented20wt% tetraethylammonium hydroxide solution was added to the reactor, followed by 60mL toluene solvent and reflux at 110℃for 6h under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P1 polymer was obtained. HGPC was used to determine its molecular weight, mn=70000, mw=154000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000112
example 2
Example 2 Compound P2 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000113
3.6mmol of phosphine oxide derivatives->
Figure BDA0002869703440000114
0.6mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000115
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P2 polymer was obtained. Determination of its fraction Using HGPCMolecular weight, mn=75000, mw=160000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000121
example 3 Compound P3 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000122
3.56mmol of phosphine oxide derivatives->
Figure BDA0002869703440000123
0.64mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000124
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P3 polymer was obtained. HGPC was used to determine its molecular weight, mn=73000, mw=141000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000125
example 4 Compound P4 and method for preparing same
Boric acid of 4.2mmol fluorene was added sequentially to a 100mL two-necked flaskEster derivative
Figure BDA0002869703440000131
3.56mmol of phosphine oxide derivatives->
Figure BDA0002869703440000132
0.64mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000133
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P4 polymer was obtained. HGPC was used to determine its molecular weight, mn=74000, mw= 155000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000134
example 5 Compound P5 and method for preparing same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000135
3.56mmol of phosphine oxide derivatives->
Figure BDA0002869703440000136
0.64mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000137
26.5 mu mol of tris (2)Methoxyphenyl) phosphine, 5 mu mol palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P5 polymer was obtained. HGPC was used to determine its molecular weight, mn=65000, mw=130000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000141
example 6 Compound P6 and method for preparing same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000142
3.56mmol of phosphine oxide derivatives->
Figure BDA0002869703440000143
0.64mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000144
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; purifying and then putting on firstPrecipitating in alcohol, filtering, and oven drying. The P6 polymer was obtained. HGPC was used to determine its molecular weight, mn=71000, mw=163000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000145
EXAMPLE 7 Compound P7 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000151
3.56mmol of phosphine oxide derivatives->
Figure BDA0002869703440000152
0.64mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000153
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P7 polymer was obtained. HGPC was used to determine its molecular weight, mn=66000, mw=145000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000154
example 8 Compound P8 and method for preparing same
Into a 100mL two-necked flask, 4.2mmol of a borate derivative of fluorene was sequentially added
Figure BDA0002869703440000155
3.56mmol of phosphine oxide derivatives->
Figure BDA0002869703440000156
0.64mmol benzocyclobutene derivatives +.>
Figure BDA0002869703440000157
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P8 polymer was obtained. HGPC was used to determine its molecular weight, mn=82000, mw= 172000.
The synthetic route for this example is as follows:
Figure BDA0002869703440000161
2. organic light-emitting diode component and preparation thereof
The structure of the organic light emitting diode component is as follows: a first electrode, an electron injection layer formed on the first electrode, an electron transport layer formed on the electron injection layer, a light emitting layer formed on the electron transport layer, a hole transport layer formed on the light emitting layer, a hole injection layer formed on the hole transport layer, a second electrode on the hole injection layer, and the electron transport layer comprises the polymeric crosslinkable compound described above, as shown in fig. 1.
Examples: ITO/ZnO (35 nm)/P1 (20 nm)/mCP Ir (ppy) 2 acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Ag(120nm)。
Wherein ZnO is used as an electron injection layer, the polymeric crosslinkable compound P1 is used as an electron transport layer, mCP is used as a main material, and Ir (ppy) 2 acac as a guest material, TAPC as a hole transport layer material and an electron blocking layer material, NPB as a hole transport layer material, HAT-CN as a hole injection layer material, and Ag as an anode.
The preparation method comprises the following steps:
firstly, cleaning an ITO substrate according to the following sequence: ultrasonic treatment with 5% KOH solution for 15min, ultrasonic treatment with pure water for 15min, ultrasonic treatment with isopropanol for 15min, and oven drying for 1h; the substrate was then transferred to a UV-OZONE apparatus for surface treatment for 15min, and immediately transferred to a glove box after the treatment. A layer of ZnO nanoparticles was spin coated on a clean ITO substrate and then baked at 120 ℃ for 15min. Dissolving a polymeric crosslinkable compound with a solvent (such as o-xylene) to form an electron transport layer material, spin-coating the electron transport layer material on a ZnO nano layer, baking the electron transport layer material at 120 ℃ for 10min to remove residual solvent, and then ring-opening crosslinking the polymer at 200 ℃ for 30-60 min; spin-coating luminous layer ink; the upper hole transport layer, the hole injection layer, and the cathode are vapor deposited by vacuum vapor deposition. Finally, the device is prepared by UV curing packaging and heating and baking for 20 min. And is denoted as "T1 device".
With reference to the above method, P2-P8 are used to replace P1, respectively, and an organic light emitting diode component is prepared as an electron transport layer material, and is respectively referred to as a "T2 component", "T3 component", … …, and a "T8 component".
Contrast device and method of making the same
The structure of the contrast device is as follows: ITO/ZnO (35 nm)/TPBi (20 nm)/mCP: ir (ppy) 2 acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Al(120nm)。
Firstly, cleaning an ITO substrate according to the following sequence: ultrasonic treatment with 5% KOH solution for 15min, ultrasonic treatment with pure water for 15min, ultrasonic treatment with isopropanol for 15min, and oven drying for 1h; the substrate was then transferred to a UV-OZONE apparatus for surface treatment for 15min, and immediately transferred to a glove box after the treatment. A layer of ZnO nanoparticles was spin coated on a clean ITO substrate and then baked at 120 ℃ for 15min. Evaporating an upper electron transport layer material TPBi in a vacuum evaporation mode, wherein the thickness is 20nm, and the evaporation rate is 0.1nm/s; after spin-coating the luminescent layer ink, evaporating a hole transport layer, a hole injection layer and a cathode by vacuum evaporation. Finally, the device is obtained by UV curing encapsulation and heating and baking for 20min, and is marked as a 'contrast device'.
The related material structure is as follows:
Figure BDA0002869703440000171
performance test:
the prepared devices were measured for light emitting performance by an IV-L test system, the model of the machine used was an F-star CS2000A instrument, and the device performance was as shown in table 1:
TABLE 1
Figure BDA0002869703440000172
Figure BDA0002869703440000181
It can be seen that the polymeric crosslinkable compound of the present invention is used as an electron transport layer material, an electron transport layer can be prepared by a solution method, and when a light emitting layer is continuously prepared on the electron transport layer by a solution method, the crosslinked polymer is insoluble in a solvent of the light emitting layer, and the performance of the prepared device is equivalent to or even exceeds that of a device formed by a conventional evaporation method. Meanwhile, the polymeric crosslinkable compound disclosed by the invention has high electron transmission capability, can effectively promote electron transmission, has good thermal stability, is suitable for constructing a thermal crosslinking electron transmission layer material, and is suitable for obtaining a large-area and low-cost OLED device through solution film formation.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (12)

1. A polymeric crosslinkable compound characterized by: has a structure shown in a general formula (I):
Figure FDA0004189128580000011
wherein:
R 1 independently selected from C1-C25 straight chain alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure FDA0004189128580000012
Ar is selected from aryl with ring atoms of 6-20;
R 3 selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 selected from single bonds, substituted or unsubstituted ring members having 6-20 aromatic groups;
L 2 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
a is an integer from 1 to 2;
b is an integer of 1 to 5;
m and n each represent the number of structural units, m: n=1:99-99:1.
2. The polymeric crosslinkable compound of claim 1 wherein: the polymeric crosslinkable compound has a structure as shown in formula (II):
Figure FDA0004189128580000013
3. the polymeric crosslinkable compound of claim 2 wherein: the polymeric crosslinkable compound has a structure represented by the general formula (II-1) or the general formula (II-2):
Figure FDA0004189128580000014
Figure FDA0004189128580000021
4. the polymeric crosslinkable compound of claim 1 wherein: ar is selected from aromatic groups with the number of ring atoms of 5-10.
5. The polymeric crosslinkable compound of claim 4 wherein: the polymeric crosslinkable compound has a structure as shown in any one of formulas (II-3) - (II-5):
Figure FDA0004189128580000022
6. the polymeric crosslinkable compound according to any one of claims 1 to 4, characterized in that: r is R 1 Independently selected from C5-C15 straight chain alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl or
Figure FDA0004189128580000031
7. The polymeric crosslinkable compound of claim 6 wherein: r is R 3 Selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
8. The polymeric crosslinkable compound according to any one of claims 1-5, characterized in that: r is R 2 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
9. A process for the preparation of a polymeric crosslinkable compound characterized by: the method comprises the following steps:
polymerizing a compound having a structure of formula a, a compound having a structure of formula B, and a compound having a structure of formula C;
Figure FDA0004189128580000032
wherein:
R 1 independently selected from C1-C25 straight chain alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure FDA0004189128580000033
Ar is selected from aryl with ring atoms of 6-20;
R 3 selected from the group consisting of C1-C25 linear alkyl groups and C3-C25 branchesAn alkanyl or C3-C25 cycloalkyl group;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
L 2 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
a is an integer from 1 to 2;
b is an integer of 1 to 5;
X 0 represents halogen.
10. The method for producing a polymerizable crosslinkable compound according to claim 9, characterized in that: the compound having the structure of formula C has a structure represented by the general formula (C-1) or (C-2):
Figure FDA0004189128580000034
11. an electron transport material characterized by: comprising the polymerizable crosslinkable compound according to any one of claims 1 to 8, or comprising the polymerizable crosslinkable compound produced by the production method according to claim 9 or 10.
12. A light-emitting diode, characterized by comprising an electron transport layer, the material of which comprises the polymeric crosslinkable compound according to any one of claims 1 to 8, or comprises the polymeric crosslinkable compound produced by the production method according to claim 9 or 10, or comprises the electron transport material according to claim 11.
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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1192223A (en) * 1995-07-28 1998-09-02 陶氏化学公司 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
JP2010155985A (en) * 2008-12-04 2010-07-15 Mitsubishi Chemicals Corp Arylamine polymer, organic light emitting device material, composition for organic light emitting device, organic light emitting device, organic el display, and organic electroluminescence illumination
CN101981086A (en) * 2008-04-02 2011-02-23 三菱化学株式会社 Polymer compound, reticulated polymer compound produced by crosslinking the polymer compound, composition for organic electroluminescent element, organic electroluminescent element, organic EL display, and organic el lighting
CN102329411A (en) * 2011-07-25 2012-01-25 华南理工大学 Water/alcohol-soluble conjugated polymer material containing crosslinkable groups and application thereof
WO2012085983A1 (en) * 2010-12-24 2012-06-28 パナソニック株式会社 Organophosphine oxide compound and process for preparing same
WO2012085988A1 (en) * 2010-12-24 2012-06-28 パナソニック株式会社 Organic el element and method for manufacturing same
CN102668156A (en) * 2009-08-18 2012-09-12 大电株式会社 Organic electroluminescent element and novel alcohol-soluble phosphorescent material
JP2013018946A (en) * 2011-07-14 2013-01-31 Mitsubishi Chemicals Corp Polymer, material for organic electroluminescent element, composition for organic electroluminescent element, organic electroluminescent element, organic el display device, and organic el light
CN103819308A (en) * 2014-03-13 2014-05-28 中国科学院上海有机化学研究所 Solidifiable poly-meta-phenylene as well as preparation method and application thereof
CN106459409A (en) * 2014-03-03 2017-02-22 三菱化学株式会社 Polymer, composition for organic electroluminescent elements, organic electroluminescent element, organic el display device, and organic el lighting device
JP2018104674A (en) * 2016-12-27 2018-07-05 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． Polymer compound, composition, liquid composition, thin film, electroluminescent element material and electroluminescent element
CN108884114A (en) * 2016-03-24 2018-11-23 三菱化学株式会社 Electronic acceptance compound and charge transmit film composition, the light-emitting component using it
WO2020009069A1 (en) * 2018-07-03 2020-01-09 保土谷化学工業株式会社 High molecular weight triarylamine compound comprising terphenyl structure in molecular main chain and organic electroluminescent element comprising said high molecular weight compound
CN111875635A (en) * 2019-09-02 2020-11-03 广东聚华印刷显示技术有限公司 Organic compound, electronic device and corresponding preparation method

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1192223A (en) * 1995-07-28 1998-09-02 陶氏化学公司 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
CN101981086A (en) * 2008-04-02 2011-02-23 三菱化学株式会社 Polymer compound, reticulated polymer compound produced by crosslinking the polymer compound, composition for organic electroluminescent element, organic electroluminescent element, organic EL display, and organic el lighting
JP2010155985A (en) * 2008-12-04 2010-07-15 Mitsubishi Chemicals Corp Arylamine polymer, organic light emitting device material, composition for organic light emitting device, organic light emitting device, organic el display, and organic electroluminescence illumination
CN102668156A (en) * 2009-08-18 2012-09-12 大电株式会社 Organic electroluminescent element and novel alcohol-soluble phosphorescent material
WO2012085983A1 (en) * 2010-12-24 2012-06-28 パナソニック株式会社 Organophosphine oxide compound and process for preparing same
WO2012085988A1 (en) * 2010-12-24 2012-06-28 パナソニック株式会社 Organic el element and method for manufacturing same
JP2013018946A (en) * 2011-07-14 2013-01-31 Mitsubishi Chemicals Corp Polymer, material for organic electroluminescent element, composition for organic electroluminescent element, organic electroluminescent element, organic el display device, and organic el light
CN102329411A (en) * 2011-07-25 2012-01-25 华南理工大学 Water/alcohol-soluble conjugated polymer material containing crosslinkable groups and application thereof
CN106459409A (en) * 2014-03-03 2017-02-22 三菱化学株式会社 Polymer, composition for organic electroluminescent elements, organic electroluminescent element, organic el display device, and organic el lighting device
CN103819308A (en) * 2014-03-13 2014-05-28 中国科学院上海有机化学研究所 Solidifiable poly-meta-phenylene as well as preparation method and application thereof
CN108884114A (en) * 2016-03-24 2018-11-23 三菱化学株式会社 Electronic acceptance compound and charge transmit film composition, the light-emitting component using it
JP2018104674A (en) * 2016-12-27 2018-07-05 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． Polymer compound, composition, liquid composition, thin film, electroluminescent element material and electroluminescent element
WO2020009069A1 (en) * 2018-07-03 2020-01-09 保土谷化学工業株式会社 High molecular weight triarylamine compound comprising terphenyl structure in molecular main chain and organic electroluminescent element comprising said high molecular weight compound
CN111875635A (en) * 2019-09-02 2020-11-03 广东聚华印刷显示技术有限公司 Organic compound, electronic device and corresponding preparation method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A phosphine oxide derivative as a universal electron transport material for organic light-emitting diodes;Jeon, SO，等;《JOURNAL OF MATERIALS CHEMISTRY》;第19卷(第33期);第5940-5944页 *
Constructing New n-Type, Ambipolar, and p-Type Aggregation-Induced Blue Luminogens by Gradually Tuning the Proportion of Tetrahphenylethene and Diphenylphophine Oxide;Mu, GY，等;《JOURNAL OF PHYSICAL CHEMISTRY C》;第118卷(第16期);第8610-8616页 *
Weakly Conjugated Phosphine Oxide Hosts for Efficient Blue Thermally Activated Delayed Fluorescence Organic Light-Emitting Diodes;Duan, K，等;《ACS APPLIED MATERIALS & INTERFACES》;第12卷(第27期);第30591-30599页 *
膦基电致发光材料及器件的研究进展;韩春苗，等;《科学通报》;第64卷(第7期);第663-681页 *

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