CN114031752A - Polymeric crosslinkable compound and preparation method and application thereof - Google Patents

Polymeric crosslinkable compound and preparation method and application thereof Download PDF

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CN114031752A
CN114031752A CN202011602574.8A CN202011602574A CN114031752A CN 114031752 A CN114031752 A CN 114031752A CN 202011602574 A CN202011602574 A CN 202011602574A CN 114031752 A CN114031752 A CN 114031752A
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crosslinkable compound
cycloalkyl
polymeric
polymeric crosslinkable
ring atoms
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CN114031752B (en
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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 shown as a general formula (I). The polymer can be dissolved in a solvent before crosslinking, and the polymer formed after crosslinking is not easily dissolved in a conventional solvent, so that the crosslinked functional layer is not easily dissolved or mixed with the next functional layer, and the performance of a device is prevented from being influenced. Moreover, the polymeric crosslinkable compound has good thermal stability at room temperature, excellent electron transport performance and higher triplet level, can realize crosslinking at high temperature without generating any by-product, and is available in soluble and liquefied OLED devicesGreat potential.

Description

Polymeric crosslinkable compound and preparation method and application thereof
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 for preparing the OLED device is a low-cost processing method, can be used for preparing large-area OLED display panels, and is currently interesting to many manufacturers. OLED devices are built up from 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, mixing between functional layers is likely to be caused, so that the performance of the device is reduced, and how to realize solution processing of multiple functional layers without affecting the performance of the device is a problem to be solved urgently. On the other hand, most of the electron transport layer materials on the market are based on vacuum evaporation type materials, and the electron transport layer materials suitable for solution processing type are few. Therefore, there remains a significant challenge to the development of fully solution processed OLED devices.
The design of the solubilized electron transport layer material is divided into two concepts: one type is a micromolecule type electron transport layer material, the structure of the micromolecule type electron transport layer material is re-modified and designed to be capable of being processed in a dissolving mode, however, the micromolecule type 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 micromolecule material has good solubility in the common organic solvent, the solvent used in the next layer is difficult to ensure not to dissolve the material deposited in the previous layer, and the solvent selection range is narrow. The other type is a polymer type electron transport layer material, and because the design idea is different from that of a small molecule electron transport layer material and the synthesis difficulty is large, the reports based on the type of material are few at present.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a polymer-type crosslinkable compound, which can be dissolved in a solvent before crosslinking, and the polymer formed after crosslinking is not easily dissolved by a conventional solvent, so that the crosslinked functional layer is not easily dissolved or mixed with the next functional layer, and the device performance is not affected. Moreover, the polymeric crosslinkable compound has good thermal stability at room temperature, excellent electron transport performance and higher triplet state energy level, can realize crosslinking at high temperature without generating any by-product, and has great potential in soluble and liquefied OLED devices.
The polymeric crosslinkable compound has a structure as represented by general formula (1):
Figure BDA0002869703440000011
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000012
Ar is selected from aromatic group with 5-20 ring atoms;
R3selected from linear alkyl of C1-C25, branched alkyl of C3-C25 or cycloalkyl of C3-C25;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a is an integer of 1 to 2;
b is an integer of 1 to 5;
m and n both represent the number of structural units, m: n is 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 with a structure shown in formula A, a compound with a structure shown in formula B and a compound with a structure shown in formula C;
Figure BDA0002869703440000021
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000022
Ar is selected from aromatic group with 5-20 ring atoms;
R3selected from linear alkyl of C1-C25, branched alkyl of C3-C25 or cycloalkyl of C3-C25;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a is an integer of 1 to 2;
b is an integer of 1 to 5;
X0represents halogen.
The present invention further relates to an electron transport material comprising the polymeric crosslinkable compound as described above, or 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 the polymeric crosslinkable compound as described above, or comprises the polymeric crosslinkable compound prepared by the above preparation method, or comprises the electron transport material as described above.
Has the advantages that:
the polymeric crosslinkable compound consists of a main chain structural unit, an electron transmission structural unit and a crosslinkable structural unit. The main chain structural unit is a fluorene structural unit with stability and solubility, the electron transmission structural unit is a phosphine oxide structural unit, and the structural unit has good electron transmission performance and good heat-resistant stability; the crosslinkable structural unit is a derivative based on a benzocyclobutene structure, and the structure has good stability at room temperature, but can be subjected to ring-opening crosslinking at high temperature. The polymeric crosslinkable compound can be dissolved in a solvent before crosslinking, and a polymer formed after crosslinking is not easily dissolved 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, maintains the excellent electron-withdrawing capability of the phosphine-oxygen 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 and liquefiable OLED devices due to the fact that crosslinking can be achieved at high temperature and no by-products are generated.
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. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
In the present invention, when the same substituent is present in multiple times, it may be independently selected from different groups. As shown in the general formula, the compound contains a plurality of R1Then R is1Can 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 art-acceptable groups including, but not limited to: c1-30Alkyl, heterocyclyl containing 3 to 20 ring atoms, aryl containing 5 to 20 ring atoms, heteroaryl containing 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and the above groups may be further substituted with art-acceptable substituents; understandably, R and R 'in-NRR' are each independently art-acceptableSubstituted by radicals, including, but not limited to H, C1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c1-6Alkyl, 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" represents 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, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same 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 mean 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 the term, e.g., "C1-9Alkyl "refers to an alkyl group containing 1 to 9 carbon atoms, which may be independently at each occurrence C1Alkyl radical, C2Alkyl radical, C3Alkyl radical, C4Alkyl radical, C5Alkyl radical, C6Alkyl radical, C7Alkyl radical, C8Alkyl or C9An 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-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexylCyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 2-ethyleicosyl group, 2-butyleicosyl group, 2-hexyleicosyl group, 2-octyleicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, adamantane and the like.
An aromatic 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. By fused ring aromatic group is meant that the rings 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. The fused heterocyclic aromatic group means a fused ring aromatic hydrocarbon group containing at least one hetero atom. For the purposes of the present invention, aromatic or heteroaromatic radicals include not only aromatic ring systems but also non-aromatic ring systems. Thus, for example, 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 systems of aromatic or heteroaromatic groups, 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, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered fused aromatic ring systems for the purposes of this invention.
In a certain preferred embodiment, the aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primates, quinazolines, quinazolinones, and derivatives thereof.
"amino" refers to a derivative of ammonia having the formula-N (X)2Wherein 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-NH2-N (alkyl)2NH (alkyl), -N (cycloalkyl)2NH (cycloalkyl), -N (heterocyclyl)2NH (heterocyclyl), -N (aryl)2NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
In the present invention, "+" attached to a single bond represents a connection or a fusion site;
in the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site;
in the present invention, when a fused site is not specified in a group, it means that an optionally fused site in the group is a fused site, and preferably two or more sites in the ortho-position in the group are fused sites;
a polymeric crosslinkable compound having a structure according to formula (I):
Figure BDA0002869703440000041
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000042
Ar is selected from aromatic group with 5-20 ring atoms;
R3selected from linear alkyl of C1-C25, branched alkyl of C3-C25 or cycloalkyl of C3-C25;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a is an integer of 1 to 2;
b is an integer of 1 to 5;
m and n both represent the number of structural units, m: n is 1:99-99: 1.
It will be appreciated that the ratio of m/n varies, the molecular structure varies and the properties vary. 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 represented by the general formula (II):
Figure BDA0002869703440000051
preferably, L1Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L1Selected from single bonds or phenyl.
Preferably, L2Selected from single bonds, substituted or unsubstitutedAn aromatic group having 5 to 10 ring atoms. More preferably, L2Selected from single bonds or phenyl.
In a preferred embodiment, the polymeric crosslinkable compound has a structure represented by the general formula (II-1) or the general formula (II-2):
Figure BDA0002869703440000052
preferably, Ar is selected from aromatic groups with 5-10 ring atoms.
More preferably, Ar is selected from phenyl. In this case, the polymerizable crosslinkable compound has a structure represented by any one of general formulae (II-3) to (II-5):
Figure BDA0002869703440000053
Figure BDA0002869703440000061
in some preferred embodiments, R1Each independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl or
Figure BDA0002869703440000062
Further preferably, R3Is selected from linear alkyl of C5-C15, branched alkyl of C5-C15 or cycloalkyl of C5-C15.
In some preferred embodiments, R2Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
The structure of the polymeric crosslinkable compound of the present invention includes, but is not limited to:
Figure BDA0002869703440000063
Figure BDA0002869703440000071
Figure BDA0002869703440000081
wherein-C6H13、-C8H17、-C12H25All represent straight chain alkyl groups.
m is 6 and n is 1, and the numbers of the structural units are not 6 and 1, but 6 parts and 1 part. Similarly, m is 11 and n is 2, and the numbers of structural units are not 11 and 2, but 11 parts and 2 parts.
The preparation method of the polymeric crosslinkable compound comprises the following steps:
polymerizing a compound with a structure shown in formula A, a compound with a structure shown in formula B and a compound with a structure shown in formula C;
Figure BDA0002869703440000082
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure BDA0002869703440000083
Ar is selected from aromatic group with 5-20 ring atoms;
R3selected from linear alkyl of C1-C25, branched alkyl of C3-C25 or cycloalkyl of C3-C25;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a is an integer of 1 to 2;
b is an integer of 1 to 5;
X0represents 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 represented by the general formula (B-1):
Figure BDA0002869703440000091
preferably, L1Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L1Selected from single bonds or phenyl.
Preferably, L2Selected from single bonds and substituted or unsubstituted aromatic groups with 5-10 ring atoms. More preferably, L2Selected from single bonds or phenyl.
In a preferred embodiment, the compound having the structure of formula C has a structure represented by the general formula (C-1) or (C-2):
Figure BDA0002869703440000092
preferably, Ar is selected from aromatic groups with 5-10 ring atoms.
More preferably, Ar is phenyl. In this case, the compound having the structure of formula A has a structure represented by any one of general formulae (A-2) to (A-4):
Figure BDA0002869703440000093
in some preferred embodiments, R1Each independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl or
Figure BDA0002869703440000094
Further preferably, R3Is selected from linear alkyl of C5-C15, branched alkyl of C5-C15 or cycloalkyl of C5-C15.
In some preferred embodiments, R2Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
An electron transport material comprises the crosslinkable polymer or the crosslinkable polymer prepared by the preparation method.
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 all functional layers thereof are prepared by printing or coating.
In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer (EML). In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL).
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 present invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., incorporating light emitting diodes according to the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In the following examples, the substituents are not specifically defined, but all represent a linear structure, i.e., -C6H13、-C8H17、-C12H25All represent straight chain alkyl groups.
In the following examples, toluene is the solvent; palladium acetate is a catalyst; tris (2-methoxyphenyl) phosphine is a catalyst ligand; tetraethyl ammonium hydroxide is alkali and plays a role in promoting reaction; phenylboronic acid is the molecule that ultimately serves as the polymer end-cap, the concept of which is that unreacted bromine groups in the polymer react with the phenylboronic acid, leaving no bromine in the polymer chain. Because the presence of bromine atoms will quench the luminescence to some extent.
1. Synthesis of Compounds
EXAMPLE 1 Compound P1 and method for its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000101
3.6mmol of phosphino derivative
Figure BDA0002869703440000102
0.6mmol of benzocyclobutene derivative
Figure BDA0002869703440000111
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is completed, the diethyl groupAdding a sodium dithiocarbamate solution into the mixed solution, 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 drying. P1 polymer was obtained. The molecular weight was determined using HGPC, Mn 70000 and Mw 154000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000112
example 2
EXAMPLE 2 Compound P2 and its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000113
3.6mmol of phosphino derivative
Figure BDA0002869703440000114
0.6mmol of benzocyclobutene derivative
Figure BDA0002869703440000115
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P2 polymer was obtained. The molecular weight of HGPC was measured, and its Mn was 75000 and Mw was 160000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000121
EXAMPLE 3 Compound P3 and method for its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000122
3.56mmol of phosphino derivative
Figure BDA0002869703440000123
0.64mmol of benzocyclobutene derivative
Figure BDA0002869703440000124
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P3 polymer was obtained. The molecular weight of HGPC was measured, and its Mn was 73000 and Mw was 141000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000125
EXAMPLE 4 Compound P4 and its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000131
3.56mmol of phosphino derivative
Figure BDA0002869703440000132
0.64mmol of benzocyclobutene derivative
Figure BDA0002869703440000133
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P4 polymer was obtained. The molecular weight of HGPC was measured and its Mn was 74000 and Mw was 155000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000134
EXAMPLE 5 Compound P5 and method for its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000135
3.56mmol of phosphino derivative
Figure BDA0002869703440000136
0.64mmol of benzocyclobutene derivative
Figure BDA0002869703440000137
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere;then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P5 polymer was obtained. The molecular weight was measured using HGPC, and its Mn was 65000 and Mw was 130000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000141
EXAMPLE 6 Compound P6 and method for its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000142
3.56mmol of phosphino derivative
Figure BDA0002869703440000143
0.64mmol of benzocyclobutene derivative
Figure BDA0002869703440000144
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P6 polymer was obtained. The molecular weight was determined using HGPC, Mn 71000 and Mw 163000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000145
EXAMPLE 7 Compound P7 and its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000151
3.56mmol of phosphino derivative
Figure BDA0002869703440000152
0.64mmol of benzocyclobutene derivative
Figure BDA0002869703440000153
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P7 polymer was obtained. The molecular weight was measured using HGPC, and its Mn was 66000 and Mw was 145000.
The synthetic route of this example is as follows:
Figure BDA0002869703440000154
EXAMPLE 8 Compound P8 and method for its preparation
4.2mmol of fluorene borate derivative was added to a 100mL two-necked flask in sequence
Figure BDA0002869703440000155
3.56mmol of phosphino derivative
Figure BDA0002869703440000156
0.64mmol of benzocyclobutene derivative
Figure BDA0002869703440000157
26.5. mu. mol of tris (2-methoxyphenyl) phosphine, 5. mu. mol of palladium acetate Pd (OAc)2Then, vacuumizing and nitrogen exchanging operation is carried out, repeating for 3 times, then adding 20 wt% tetraethylammonium hydroxide solution by using an injector, then adding 60mL toluene solvent, and refluxing for 6h at 110 ℃ under the nitrogen atmosphere; then 4mmol of phenylboronic acid is added into the mixed solution, and the reaction is continued for 12 hours. After the reaction is finished, adding a sodium diethyldithiocarbamate solution into the mixed solution, 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 drying. P8 polymer was obtained. The molecular weight of HGPC was measured and found to be 82000 Mn and 172000 Mw.
The synthetic route of 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 includes the above-mentioned polymerization type crosslinkable compound, as shown in fig. 1.
Example (c): ITO/ZnO (35nm)/P1(20nm)/mCP Ir (ppy)2acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Ag(120nm)。
Wherein ZnO is used as an electron injection layer, a polymeric crosslinkable compound P1 is used as an electron transport layer, mCP is used as a host material,Ir(ppy)2acac is used as a guest material, TAPC is used as a hole transport layer material and an electron blocking layer material, NPB is used as a hole transport layer material, HAT-CN is used as a hole injection layer material, and Ag is used as an anode.
The preparation method comprises the following steps:
firstly, the ITO substrate is cleaned according to the following sequence: 5% KOH solution is subjected to ultrasonic treatment for 15min, pure water is subjected to ultrasonic treatment for 15min, isopropanol is subjected to ultrasonic treatment for 15min, and the mixture is dried in an oven for 1 h; the substrate was then transferred to a UV-ozon apparatus for surface treatment for 15min and immediately transferred to a glove box after treatment. And (3) spin-coating a layer of ZnO nanoparticles on a clean ITO substrate, and then baking for 15min at the temperature of 120 ℃. Dissolving a polymeric crosslinkable compound by using a solvent (such as o-xylene) to serve as an electron transport layer material, spin-coating the electron transport layer material on a ZnO nano layer, baking at 120 ℃ for 10min to remove residual solvent after the electron transport layer material is spin-coated, and then performing ring-opening crosslinking on a polymer at 200 ℃ for 30-60 min; spin coating with luminescent layer ink; and evaporating the upper hole transport layer, the hole injection layer and the cathode in a vacuum evaporation mode. And finally, carrying out UV curing packaging, and heating and baking for 20min to prepare the device. Denoted as "T1 device".
Referring to the above method, P2-P8 are respectively used to replace P1 and used as electron transport layer material to prepare organic light emitting diode devices, which are respectively referred to as "T2 device", "T3 device", … … "T8 device".
Contrast device and preparation method thereof
The structure of the comparison device is as follows: ITO/ZnO (35nm)/TPBi (20nm)/mCP Ir (ppy)2acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Al(120nm)。
Firstly, the ITO substrate is cleaned according to the following sequence: 5% KOH solution is subjected to ultrasonic treatment for 15min, pure water is subjected to ultrasonic treatment for 15min, isopropanol is subjected to ultrasonic treatment for 15min, and the mixture is dried in an oven for 1 h; the substrate was then transferred to a UV-ozon apparatus for surface treatment for 15min and immediately transferred to a glove box after treatment. And (3) spin-coating a layer of ZnO nanoparticles on a clean ITO substrate, and then baking for 15min at the temperature of 120 ℃. Evaporating an electron transport layer material TPBi in a vacuum evaporation mode, wherein the thickness is 20nm, and the evaporation rate is 0.1 nm/s; after spin coating the ink of the light-emitting layer, the hole transport layer, the hole injection layer and the cathode are evaporated by vacuum evaporation. Finally, packaging through UV curing, and heating and baking for 20min to obtain a device, which is recorded as a contrast device.
The material structure involved is as follows:
Figure BDA0002869703440000171
and (3) performance testing:
the prepared devices were tested for their luminescence properties by an IV-L test system using an F-star CS2000A instrument, the device properties are shown in table 1:
TABLE 1
Figure BDA0002869703440000172
Figure BDA0002869703440000181
Therefore, when the polymeric crosslinkable compound is used as an electron transport layer material, the electron transport layer can be prepared by a solution method, and when a luminescent layer is prepared on the electron transport layer by the solution method, the crosslinked polymer is insoluble in a solvent of the luminescent layer, so that the performance of the prepared device is equivalent to or even superior to that of the device of the conventional electron transport layer formed by an evaporation method. Meanwhile, the polymeric crosslinkable compound has high electron transport capacity, can effectively promote the transport of electrons, has good thermal stability, is suitable for constructing a thermal crosslinking electron transport layer material, and is suitable for obtaining large-area and low-cost OLED devices through solution film formation.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (12)

1. A polymeric crosslinkable compound characterized by: having the structure of formula (I):
Figure FDA0002869703430000011
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure FDA0002869703430000012
Ar is selected from aromatic group with 5-20 ring atoms;
R3selected from linear alkyl of C1-C25, branched alkyl of C3-C25 or cycloalkyl of C3-C25;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a is an integer of 1 to 2;
b is an integer of 1 to 5;
m and n both represent the number of structural units, m: n is 1:99-99: 1.
2. A polymeric crosslinkable compound according to claim 1, wherein: the polymeric crosslinkable compound has a structure represented by the general formula (II):
Figure FDA0002869703430000013
3. a polymeric crosslinkable compound according to claim 2, wherein: the polymeric crosslinkable compound has a structure represented by the general formula (II-1) or the general formula (II-2):
Figure FDA0002869703430000014
Figure FDA0002869703430000021
4. a polymeric crosslinkable compound according to claim 1, wherein: and Ar is selected from aromatic group with 5-10 ring atoms.
5. A polymeric crosslinkable compound of claim 4, wherein: the polymeric crosslinkable compound has a structure represented by any one of general formulas (II-3) to (II-5):
Figure FDA0002869703430000022
6. a polymeric crosslinkable compound according to any one of claims 1 to 4, wherein: r1Are respectively and independentlySelected from the group consisting of C5-C15 linear alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl or
Figure FDA0002869703430000031
7. A polymeric crosslinkable compound according to claim 6, wherein: r3Is selected from linear alkyl of C5-C15, branched alkyl of C5-C15 or cycloalkyl of C5-C15.
8. A polymeric crosslinkable compound according to any one of claims 1 to 5, wherein: r2Are respectively and independently selected from C5-C15 linear alkyl, C5-C15 branched alkyl or C5-C15 cycloalkyl.
9. A method for preparing a polymerizable crosslinkable compound, characterized by: the method comprises the following steps:
polymerizing a compound with a structure shown in formula A, a compound with a structure shown in formula B and a compound with a structure shown in formula C;
Figure FDA0002869703430000032
wherein:
R1each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl or
Figure FDA0002869703430000033
Ar is selected from aromatic group with 5-20 ring atoms;
R3selected from linear alkyl of C1-C25, branched alkyl of C3-C25 or cycloalkyl of C3-C25;
R2each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl or C3-C25 cycloalkyl;
L1selected from single bond, substituted or unsubstituted ring with 5-20 atomic numberAn aromatic group;
L2selected from single bond, substituted or unsubstituted aromatic group with 5-20 ring atoms;
a is an integer of 1 to 2;
b is an integer of 1 to 5;
X0represents halogen.
10. A method of preparing a polymeric crosslinkable compound according to claim 9, characterized in that: the compound with the structure of the formula C has the structure shown as a general formula (C-1) or (C-2):
Figure FDA0002869703430000034
11. an electron transport material, comprising: comprising a polymeric crosslinkable compound according to any one of claims 1 to 8 or comprising a polymeric crosslinkable compound prepared by the preparation process according to claim 9 or 10.
12. A light-emitting diode comprising an electron transport layer, wherein a material of the electron transport layer comprises the polymeric crosslinkable compound according to any one of claims 1 to 8, or comprises the polymeric crosslinkable compound prepared by the preparation method according to claim 9 or 10, or comprises the electron transport material according to claim 11.
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