WO2018113783A1 - Compound containing cross-linking group and use thereof - Google Patents

Compound containing cross-linking group and use thereof Download PDF

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WO2018113783A1
WO2018113783A1 PCT/CN2017/118065 CN2017118065W WO2018113783A1 WO 2018113783 A1 WO2018113783 A1 WO 2018113783A1 CN 2017118065 W CN2017118065 W CN 2017118065W WO 2018113783 A1 WO2018113783 A1 WO 2018113783A1
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group
carbon atoms
alkane
organic
crosslinking
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PCT/CN2017/118065
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French (fr)
Chinese (zh)
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潘君友
于明泉
杨曦
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广州华睿光电材料有限公司
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Priority to CN201780059502.3A priority Critical patent/CN109843854B/en
Publication of WO2018113783A1 publication Critical patent/WO2018113783A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/90—Benzo [c, d] indoles; Hydrogenated benzo [c, d] indoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to the field of electronics, and in particular to a compound containing a crosslinking group and uses thereof.
  • OLEDs Organic Light-Emitting Diodes
  • OLEDs Organic Light-Emitting Diodes since its invention
  • OLEDs Organic Light-Emitting Diodes
  • Due to the diversity of organic materials in synthesis Sex relatively low manufacturing costs and excellent optical and electrical properties have great potential for applications in optoelectronic devices such as flat panel displays and lighting
  • optoelectronic devices such as flat panel displays and lighting
  • OLED devices mostly use a multilayer device structure, that is, in addition to the light-emitting layer, one or more layers of hole transport/injection layers or electron transport/injection layers. Therefore, in addition to the development of excellent luminescent materials, the development of excellent electron transport/injection materials and hole transport/injection materials is also the key to achieving high performance OLEDs (J Mater Chem, 2008, 18: 4495-4509.; Acc Chem Res, 2005). , 38: 632-643.; Adv Mater, 2007, 19: 810-814).
  • organic photoelectric materials have similar solubility, that is, organic/polymer luminescent materials, hole injection/transport materials, electron injection/transport materials in toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene, tetrahydrofuran, etc. It has good solubility in organic solvents. Therefore, when solution processing methods are used to prepare multilayer and complex OLEDs, there are problems such as interface miscibility and interface corrosion.
  • crosslinking groups such as perfluorocyclobutane, styryl, butylene oxide, silicone, acrylate, benzocyclobutenyl are employed.
  • the crosslinking group on the polymer can initiate a crosslinking group perfluorocyclobutane (Adv. Funct. Mater., 2002, 12, 745) and a styryl group under conditions of light, heat, and the like.
  • butylene oxide Nature, 2003, 421, 829.
  • silicone based Acc. Chem. Res., 2005, 38, 632
  • acrylate group Chem. Mater., 2003).
  • the crosslinkable polymers reported so far are based on conjugated polymers.
  • Most conjugated polymers have lower triplet energy levels, which quench adjacent luminescent layers, such as excitons with higher triplet energy (relatively shorter wavelengths) in the green luminescent layer, and do not To the role of the exciton blocking layer. These all restrict the improvement of the performance of OLED devices and cannot meet the actual needs.
  • the crosslinking group-containing compound of one embodiment has the following structural formula (I):
  • SG has the structural formula (II):
  • Ar is an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms;
  • CLG is a crosslinking group
  • o 0 or 1
  • p is an integer greater than or equal to 2;
  • R 1 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , a linear alkane having 1 to 10 carbon atoms, and total An alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having 3 to 10 total carbon atoms, and a cycloalkane group having 3 to 10 total carbon atoms;
  • R 2 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms.
  • -L- is a single bond or a conjugated aryl group having 5 to 40 carbon atoms
  • Ar 1 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms.
  • Y is an integer from 0 to 5
  • Ar 0 is selected from one of the following structural formulae:
  • Ar 2 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
  • X is an integer from 0 to 4, and X1 is an integer from 0 to 3.
  • n is selected from an integer of 0 to 10
  • R 9 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 14 ) 2 , Si(R 14 ) 3 , a linear alkane having 1 to 10 carbon atoms, and a total carbon atom.
  • the number is from 1 to 10, an alkane ether, an alkane sulfide having a total carbon number of from 1 to 10, a branched alkane having a total carbon number of from 3 to 10, a cycloalkane having a total carbon number of from 3 to 10, and R 14 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
  • the dotted line in Structural Formula III indicates that L is bonded to Ar 0
  • the dotted line and circle in Structural Formula (IIIa) indicate that L can be bonded to any carbon atom of two benzene rings in the circle or an aromatic ring or heteroaryl ring contained in the structural formula of Ar 2 .
  • Any carbon atom linkage, the dashed lines in structural formula (IIIb) and structural formula (IIIc) all indicate that L can be attached to any carbon atom of the benzene ring through which the dotted line passes.
  • the above-mentioned compound containing a crosslinking group contains an organic functional structural unit and a crosslinkable group, and has good solubility and film formability.
  • the compound can be crosslinked by heat treatment or ultraviolet irradiation to crosslink the intermolecular crosslinkable groups, thereby curing the compound to form a film.
  • the composition containing the compound since the above compound has good solubility and film forming property, the composition containing the compound has good printability and film-forming property, thereby making the electronic device containing the compound or the composition high. The performance ultimately makes the manufacturing cost of the electronic device low and efficient.
  • FIG. 1 is a schematic structural view of an organic light emitting diode according to an embodiment.
  • the aryl group means a hydrocarbon group containing at least one aromatic ring, including a monocyclic aryl group and a polycyclic aryl group, unless otherwise specified.
  • the polycyclic aryl group may also be a fused aryl group, that is, an aryl group having two or more rings, and wherein two adjacent rings share two carbon atoms (ie, a fused ring).
  • the aryl group may be, for example, benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, snail or a derivative thereof.
  • H in the aryl group is substituted by a substituent, it is also considered to be an aryl group in the present embodiment.
  • Heteroaryl refers to an aromatic radical containing at least one heteroatom, including monocyclic heteroaryl and polycyclic heteroaryl.
  • the hetero atom may be, for example, at least one selected from the group consisting of Si, P, O, N, S, and Ge; further, the hetero atom is selected from at least one of Si, P, O, N, and S; The hetero atom is selected from at least one of O, N and S.
  • the polycyclic heteroaryl group may also be a heteroaromatic group, that is, a fused aryl group containing at least one hetero atom.
  • the heteroaryl group may, for example, be furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, Anthracene, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine , pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone or a derivative thereof.
  • the aryl or heteroaryl group may further include a group in which at least two aromatic rings or heteroaromatic rings are bonded by a non-aromatic ring group, wherein the number of non-H atoms in the non-aromatic ring group is less than 10 %. In one embodiment, the number of non-H atoms in the non-aromatic ring group is less than 5%. In one embodiment, the non-aromatic ring group is a C atom, an N atom or an O atom.
  • the crosslinking group-containing compound of one embodiment has the following structural formula (I):
  • SG has the structural formula (II):
  • Ar is an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms;
  • CLG is a crosslinking group
  • o 0 or 1
  • p is an integer greater than or equal to 2;
  • R 1 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , a linear alkane having 1 to 10 carbon atoms, and total An alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having 3 to 10 total carbon atoms, and a cycloalkane R 2 having 3 to 10 total carbon atoms.
  • H, D an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
  • -L- is a single bond or a conjugated aryl group having 5 to 40 carbon atoms
  • Ar 1 is an aromatic group having 5 to 40 ring atoms or a heteroaromatic group having 5 to 40 ring atoms.
  • Y is an integer from 0 to 5
  • Ar 0 is selected from one of the following structural formulae:
  • Ar 2 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
  • X is an integer from 0 to 4, and X1 is an integer from 0 to 3.
  • n is selected from an integer of 0 to 10
  • R 9 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 14 ) 2 , Si(R 14 ) 3 , a linear alkane having 1 to 10 carbon atoms, and a total carbon atom.
  • Alkane ether having a number of 1 to 10 an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and a cycloalkane having a total carbon number of 3 to 10, each of which is a base.
  • R 14 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms.
  • the dotted line in the structural formula III indicates that L is bonded to Ar 0
  • the dotted line and the circle in the structural formula (IIIa) indicate that the L can be combined with any carbon atom of the two benzene rings in the circle or the structural formula of Ar 2 .
  • any carbon atom of the aromatic or heteroaromatic ring is bonded, and the dotted lines in the structural formula (IIIb) and the structural formula (IIIc) each indicate that L can be attached to any carbon atom of the benzene ring through which the dotted line passes.
  • Ar is an aryl group having 6 to 20 ring atoms or a heteroaryl group having 6 to 20 ring atoms. Further, Ar is an aryl group having 6 to 16 ring atoms or a heteroaryl group having 6 to 16 ring atoms. Further, Ar is an aryl group having 6 to 12 ring atoms or a heteroaryl group having 6 to 12 ring atoms.
  • Ar is a substituted aryl group having 6 to 20 ring atoms or a substituted heteroaryl group having 6 to 20 ring atoms. Further, Ar is a substituted aryl group having 6 to 16 ring atoms or a substituted heteroaryl group having 6 to 16 ring atoms. Further, Ar is a substituted aryl group having 6 to 12 ring atoms or a substituted heteroaryl group having 6 to 12 ring atoms.
  • Ar is an aryl group having 5 to 18 ring atoms or a heteroaryl group having 5 to 18 ring atoms. Further, Ar is an aryl group having 5 to 15 ring atoms or a heteroaryl group having 5 to 15 ring atoms. Further, Ar is an aryl group having 5 to 18 ring atoms or a heteroaryl group having 5 to 15 ring atoms.
  • Ar is a substituted aryl group having 5 to 18 ring atoms or a substituted heteroaryl group having 5 to 18 ring atoms. Further, Ar is a substituted aryl group having 5 to 15 ring atoms or a substituted heteroaryl group having 5 to 15 ring atoms. Further, Ar is a substituted aryl group having 5 to 18 ring atoms or a substituted heteroaryl group having 5 to 15 ring atoms.
  • Ar is selected from the group consisting of benzene, biphenyl, triphenyl, benzo, anthracene, anthracene, and derivatives thereof.
  • Ar is selected from the group consisting of triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, anthracene Carbazole, pyridinium, pyrrole parallel pyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyridyl Oxazine, triazine, oxazine, oxazine, oxadiazine, hydrazine, benzimidazole, oxazole, benzoxazole, dibenzoxazole, isoxazole, benzothiazole, quinoline
  • Ar is selected from one of the following structural formulae:
  • -R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each independently selected from the group consisting of H, D, F, -CN, -NO 2 , -CF 3 , alkenyl, alkynyl , an amine group, an acyl group, an amide group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, carbon An aryl group having 6 to 60 atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused ring aryl group having 7 to 60 carbon atoms, a fused heterocyclic aryl group having 4 to 60 carbon atoms, and the above One of the combination groups formed by at least two interconnections in the
  • -R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a single ring.
  • -R 15 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 16 , -R 17 , -R 18 , -R 19 and -R 20 , respectively.
  • -R 20 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 16 , -R 17 , -R 18 , -R 19 and -R 15 , respectively.
  • -R 16 and -R 17 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • -R 18 and -R 19 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • -R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each independently selected from substituted alkyl groups having 1 to 60 carbon atoms, and carbon atoms. a substituted cycloalkyl group of 3 to 60, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, or a substituted fused ring having 7 to 60 carbon atoms. An aryl group or a substituted fused heterocyclic aryl group having 4 to 60 carbon atoms.
  • the CLG is a cyclic monoalkenyl group, a linear monoalkenyl group, a linear dienyl group, an alkynyl group, an alkenyloxy group, a dienyloxy group, an acrylic group, an oxypropylene group, an epoxy group Alkyl, silane or cyclobutane.
  • CLG enables a compound containing a crosslinking group to undergo a crosslinking reaction, thereby increasing the solvent resistance of the compound containing a crosslinking group.
  • CLG can It is sufficient to crosslink the CL-containing compound between the compounds containing a crosslinking group in an environment of at least 100 ° C, water and oxygen.
  • the above crosslinking reaction can be enhanced by illumination. Further, the above crosslinking reaction can be enhanced by UV light (i.e., ultraviolet light).
  • the CLG is selected from one of the following groups:
  • R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 21 ) 2 , Si(R 21 ) 3 , carbon a linear alkane having 1 to 10 atoms, an alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and total One of the cycloalkanes having 3 to 10 carbon atoms, R 21 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a ring atom number 5 to 10 heteroaryl groups;
  • Ar 12 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
  • s is an integer greater than or equal to 0, and t is an integer greater than or equal to 0;
  • o is zero.
  • o is one.
  • p is an integer from 2 to 20. Further, p is an integer of 2 to 10. Further, p is an integer of 2-8. Further, p is an integer of 2 to 5. Further, p is an integer of 3 to 4.
  • -L- is a linking group, a single bond or a conjugated aryl group having 5 to 40 carbon atoms.
  • L is a conjugated aryl group substituted with R 22 having 5 to 40 carbon atoms
  • L is a linking group having a phenyl ring.
  • X3 is an integer from 0 to 4.
  • Ar 1 and Ar 2 are each independently selected from an aryl group having 6 to 40 ring atoms or a heteroaryl group having 6 to 30 ring atoms. Further, Ar 1 and Ar 2 are each independently selected from an aryl group having 6 to 30 ring atoms or a heteroaryl group having 6 to 30 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 6 to 25 ring atoms or a heteroaryl group having 6 to 25 ring atoms.
  • L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 30 ring atoms or a heteroaryl group having 5 to 30 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 15 ring atoms or a heteroaryl group having 5 to 15 ring atoms.
  • the above aryl group contains 6 to 15 carbon atoms. Further, the above aryl group contains 6 to 10 carbon atoms. Further, the above heteroaryl group contains 2 to 15 carbon atoms. Further, the above heteroaryl group contains 2 to 10 carbon atoms and at least one hetero atom, provided that the total number of carbon atoms and hetero atoms is at least 4.
  • L, Ar 1 and Ar 2 are each independently selected from one of the following groups:
  • -R 30 , -R 31 , -R 32 , -R 33 , -R 34 and -R 35 are each independently selected from the group consisting of H, D, F, -CN, -NO 2 , -CF 3 , alkenyl, alkynyl , an amine group, an acyl group, an amide group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, carbon An aryl group having 6 to 60 atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused ring aryl group having 7 to 60 carbon atoms, a fused heterocyclic aryl group having 4 to 60 carbon atoms, and the above One of the combination groups formed by at least two interconnections in the
  • -R 30 , -R 31 , -R 32 , -R 33 , -R 34 and -R 35 are each capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a single ring.
  • -R 35 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 30 , -R 31 , -R 32 , -R 33 and -R 34 , respectively.
  • -R 20 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 16 , -R 17 , -R 18 , -R 19 and -R 15 , respectively.
  • -R 31 and -R 32 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • -R 33 and -R 34 are capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • -R 30 , -R 31 , -R 32 , -R 33 , -R 34 and -R 35 are each independently selected from substituted alkyl groups having 1 to 60 carbon atoms, and carbon atoms. a substituted cycloalkyl group of 3 to 60, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, or a substituted fused ring having 7 to 60 carbon atoms. An aryl group or one of the substituted fused heterocyclic aryl groups having 4 to 60 carbon atoms.
  • L, Ar 1 and Ar 2 are each independently selected from one of the following structural formulae:
  • the number below the structural formula (such as C36) only represents the serial number of the corresponding structural formula, and has no other meanings.
  • one structural formula represents a substance, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other significance;
  • -R 3 is selected from -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , B(OR 40 ) 2 , Si(R 40 ) 3 , linear An alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, or an aryl group having a cycloalkane having 6 to 10 carbon atoms, and R 40 is H, D, and having 1 carbon atom.
  • u is selected from one of integers from 0 to 2
  • v is selected from one of integers from 0 to 3
  • w is selected from one of integers from 0 to 4
  • t is selected from one of integers from 0 to 5;
  • Z does not exist and the structural formula of A is:
  • X4 is selected from one of integers from 0 to 5, and the other symbols have the same meanings as indicated above.
  • R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 25 ) 2 , Si(R 25 ) 3 , carbon a linear alkane having 1 to 10 atoms, an alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and total One of the groups of a cycloalkane having 3 to 10 carbon atoms, R 25 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aromatic hydrocarbon group, and a ring number of 5 to 5 An aryl group having 10 or a heteroaryl group having 5 to 10 ring atoms; a broken line in the above group indicates that Z can be bonded to two benzene rings in the structural formula I of Ar 0 .
  • the structural formula of A is selected from one of the following structures:
  • one structural formula represents an A, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other meaning.
  • the SG is selected from one of the following structural formulae:
  • R 8 is selected from a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms; a branched alkyl group of ⁇ 20, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a thioalkoxy group having 3 to 20 carbon atoms, and a carbon number a silyl group of 3 to 20, a ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, and a cyano group.
  • n is an integer greater than 0;
  • R 8 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group by itself.
  • R 8 is a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms or a carbon atom. The number is 3 to 20 alkoxy groups.
  • L 1 is aryl or heteroaryl. In one embodiment, L 1 is selected from one of the following structural formulae:
  • the individual H atom or CH 2 group of formula I can be substituted with L 1 .
  • R 41 is an alkyl group having 1 to 40 C atoms.
  • R 41 is selected from one of the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclo Butyl, methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl , pentafluoroethyl, trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cycl
  • the alkoxy group having 1 to 40 C atoms is a methoxy group, a trifluoromethoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, or a secondary group. Butoxy, tert-butoxy or methylbutoxy.
  • the above-mentioned compound containing a crosslinking group is a small molecule, that is, a molecule which is not a polymer, an oligomer, a dendrimer or a copolymer.
  • the above-mentioned compound containing a crosslinking group has a hole transporting function, so that the compound can be applied to an organic electronic device. Further, the above-mentioned compound containing a crosslinking group can be used as a material of a hole transport layer in an OLED.
  • the above-mentioned compound containing a crosslinking group has a high LUMO (Lowest Un°Ccupied Molecular Orbital) level, so that the compound has an electron blocking function and can be used for organic electrons.
  • the above-mentioned compound containing a crosslinking group can be used as a material of an electron blocking layer in an OLED.
  • the higher LUMO energy level in the present embodiment means that the LUMO energy level of the functional layer containing the compound is higher than the LUMO energy level of the adjacent functional layer, for example, in the OLED, when the compound is used as an electron.
  • the LUMO energy level of the electron blocking layer is higher than the LUMO energy level of the light emitting layer.
  • the above-mentioned compound containing a crosslinking group has a higher triplet level (T 1 ), so that the compound has a triplet exciton blocking function and can be used in an organic electronic device.
  • the above-mentioned compound containing a crosslinking group can be used as a material of an exciton blocking layer in an OLED.
  • T 1 of the present embodiment refers to a functional layer of the compound is higher than T 1 T adjacent functional layer 1, the phosphorescent OLED for example, when the compound as an exciton blocking the material layer, the exciton blocking layer is higher than the T 1 T 1 of the light emitting layer.
  • the above-described compound containing a crosslinking group has a higher singlet energy level S 1 , so that the compound has a singlet exciton blocking function and can be used in an organic electronic device.
  • the above-mentioned compound containing a crosslinking group can be used as a material of an exciton blocking layer in an OLED.
  • higher S S 1 refers to the compound containing the functional layer 1 is higher than the adjacent functional layers S 1, for example, a fluorescent OLED when the exciton blocking compound the material layer, the exciton blocking layer is greater than S 1 S 1 of the light emitting layer.
  • the compound of formula (I-1) has a higher LUMO. Further, the compound of the formula (I-1) is greater than or equal to -2.7 eV. Further, the compound of the formula (I-1) is greater than or equal to -2.6 eV. Further, the compound of the formula (I-1) is greater than or equal to -2.5 eV. Further, the compound of the formula (I-1) is greater than or equal to -2.4 eV.
  • the HOMO of the compound of formula (I-1) is less than or equal to -5.0 eV, wherein HOMO represents the highest occupied orbital. Further, the compound of the formula (I-1) has a HOMO of less than or equal to -5.1 eV. Further, the compound of the formula (I-1) has a HOMO of less than or equal to -5.2 eV.
  • (HOMO-1)-HOMO of the compound of formula (I-1) is greater than or equal to 0.3 eV, wherein (HOMO-1) represents the second highest occupied orbital. Further, the compound of the formula (I-1) has a (HOMO-1)-HOMO of greater than or equal to 0.35 eV. Further, the compound of the formula (I-1) has a (HOMO-1)-HOMO of greater than or equal to 0.4 eV. Further, the (HOMO-1)-HOMO of the compound of the formula (I-1) is greater than or equal to 0.45 eV.
  • the compound of formula (I-1) has a triplet energy level (T 1 ) greater than or equal to 2.5 eV. Further, the compound of the formula (I-1) has a T 1 greater than or equal to 2.6 eV. Further, the compound of the formula (I-1) has a T 1 greater than or equal to 2.7 eV.
  • both the HOMO level and the LUMO level can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy), and both can pass CV (cyclic voltammetry)
  • photoelectric effect such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy)
  • UPS UV photoelectron spectroscopy
  • the measurement can also be carried out by quantum chemical methods such as DFT (density functional theory).
  • the triplet energy level T1 can be measured by low temperature time resolved luminescence spectroscopy or by quantum simulation, for example by Time-dependent DFT simulation or by commercial software Gaussian 03W (Gaussian Inc.). Calculation. Among them, the specific simulation method can be found in WO2011141110.
  • the absolute values of HOMO, LUMO, and T1 depend on the measurement method, calculation method, or evaluation method used. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the energy level values determined by different methods should be calibrated against each other.
  • the values of HOMO, LUMO, and T1 are simulations based on Time-dependent DFT, but do not affect the application of other measurement methods or calculation methods.
  • the total amount of SP 3 hybridized groups in the compound containing a crosslinking group is less than or equal to 30% of the total molecular weight.
  • the presence of fewer SP 3 hybrid groups is effective to ensure the thermal stability of the above-described crosslinking group-containing compound, thereby ensuring the stability of the device including the compound.
  • the total amount of the SP 3 hybridized group is less than or equal to 20% of the total molecular weight.
  • the total amount of the SP 3 hybridized group is less than or equal to 10% of the total molecular weight.
  • the crosslinking group-containing compound has a glass transition temperature of less than or equal to 100 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 120 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 140 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 160 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 180 °C.
  • the compound having a crosslinking group has a molar mass of greater than or equal to 700 g/mol, so that the compound can be used as a raw material for a printed OLED. Further, the molar mass is greater than or equal to 800 g/mol. Further, the compound having a crosslinking group has a molar mass of greater than or equal to 900 g/mol. Further, the compound having a crosslinking group has a molar mass of greater than or equal to 1000 g/mol. Further, the compound having a crosslinking group has a molar mass of greater than or equal to 1100 g/mol.
  • the compound containing a crosslinking group has a solubility in toluene of greater than or equal to 10 mg/mL at 25 °C. Further, the compound having a crosslinking group has a solubility in toluene at 25 ° C of 15 mg/mL or more. The compound containing a crosslinking group has a solubility in toluene of greater than or equal to 20 mg/mL at 25 °C.
  • the structural formula of the compound containing a crosslinking group is selected from one of the following structural formulae:
  • one structural formula represents a substance, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other meaning.
  • the above-mentioned compound containing a crosslinking group contains an organic functional structural unit and a crosslinkable group, and has good solubility and film formability.
  • the compound can be crosslinked by heat treatment or ultraviolet irradiation to crosslink the intermolecular crosslinkable groups, thereby curing the compound to form a film.
  • the composition containing the compound since the above compound has good solubility and film-forming property, the composition containing the compound has good printability and film-forming property, thereby making the electronic device containing the compound or the composition longer. The longevity and high performance ultimately result in low manufacturing cost and high efficiency of the electronic device;
  • the above-mentioned compound containing a crosslinking group has a hole transporting function, so that the compound can be applied to an organic electronic device;
  • the above-mentioned compound containing a crosslinking group has a high LUMO energy level, so that the compound has an electron blocking function and can be used in an organic electronic device;
  • the above compound having a crosslinking group has a higher triplet energy level, so that the compound has a triplet exciton blocking function and can be used in an organic electronic device;
  • the above compound having a crosslinking group has a higher singlet energy level, so that the compound has a singlet exciton blocking function and can be used in an organic electronic device;
  • the total amount of the SP 3 hybridized group is less than or equal to 30% of the total molecular weight, and the presence of a small amount of the SP 3 hybrid group can effectively ensure the above-mentioned crosslinking.
  • the thermal stability of the compound of the group thereby ensuring the stability of the device comprising the compound.
  • the reaction may be carried out using a raw material containing a reactive group.
  • the active group-containing raw material comprises the structural unit A and the structural unit SG and at least one leaving group in the structural formula (I) of the above-mentioned compound having a crosslinking group.
  • the leaving group is bromine, iodine, boric acid or a boronic ester.
  • reaction for forming a C-C linkage is a reaction well known to those skilled in the art and will not be described herein. Further, the reaction that forms a C-C linkage is a coupling reaction. Further, the reaction for forming a C-C linkage is a SUZUKI coupling reaction (Suzuki reaction), a STILLE coupling reaction (Stiler reaction) or a HECK coupling reaction (Heck reaction).
  • the mixture of one embodiment includes the crosslinking group-containing compound and the organic functional material of the above embodiment.
  • the organic functional material is selected from the group consisting of hole injection materials (HIM), hole transport materials (HTM), hole blocking materials (HBM), electron injecting materials (EIM), electron transport materials (ETM), At least one of an electron blocking material (EBM), an organic matrix material (Host), a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant), a thermally excited delayed fluorescent material (TADF material), and an organic dye One. .
  • HIM hole injection materials
  • HTM hole transport materials
  • HBM hole blocking materials
  • EIM electron injecting materials
  • ETM electron transport materials
  • an organic matrix material Host
  • a singlet illuminant fluorescent illuminant
  • a triplet illuminant phosphorescent illuminant
  • TADF material thermally excited delayed fluorescent material
  • the mixture comprises the above-described compound containing a crosslinking group and a fluorescent illuminant. It should be noted that the above-mentioned compound containing a crosslinking group may be used as a host material or as a host material together with other materials.
  • the mixture comprises the above-described compound containing a crosslinking group and a TADF material.
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet illuminant is a monostyrylamine, a dibasic styrylamine, a ternary styrylamine, a quaternary styrylamine, a styrene phosphine, a styrene ether or an aromatic amine.
  • the monostyrylamine is a compound containing an unsubstituted or substituted styryl group and at least one amine. Further, the amine in the monobasic styrene amine is an aromatic amine.
  • the binary styrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine. Further, the amine in the dibasic styrylamine is an aromatic amine.
  • the ternary styrylamine is a compound containing three unsubstituted or substituted styryl groups and at least one amine. Further, the amine in the ternary styrylamine is an aromatic amine.
  • the quaternary styrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine. Further, the amine in the tetrabasinamine is an aromatic amine.
  • Styrene phosphine is a compound comprising a styryl group and at least one phosphine.
  • the styrene ether comprises a compound of a styryl group and at least one ether.
  • the styryl group is a distyryl group. It should be noted that a substituted distyryl group can also be used as the styryl group of the present embodiment.
  • the aromatic amine is a compound containing three unsubstituted or substituted aryl groups directly bonded to nitrogen or three unsubstituted or substituted heteroaryl groups directly bonded to nitrogen. Further, the aryl or heteroaryl group in the aromatic amine contains at least one fused ring, and the number of ring atoms in the aryl or heteroaryl group is at least 14. Further, the aromatic amine is an aromatic guanamine, an aromatic guanidine diamine, an aromatic guanamine, an aromatic guanidine diamine, an aromatic thiamine or an aromatic quinone diamine.
  • Aromatic decylamine is a compound in which a binary aromatic amine group is directly bonded to hydrazine.
  • the aromatic decylamine is a compound in which a binary aromatic amine group is directly bonded to the carbon atom No. 9 of hydrazine.
  • An aromatic quinone diamine is a compound in which two diaryl arylamine groups are directly attached to hydrazine.
  • the aromatic guanamine is a compound in which two binary aromatic amine groups are bonded to the carbon atoms of No. 9 and No. 10, respectively.
  • Aromatic decylamine is a compound in which a binary aromatic amine group is directly bonded to hydrazine.
  • the aromatic decylamine is a compound in which a divalent aromatic amine group is directly bonded to the carbon atom No. 1 of hydrazine.
  • An aromatic quinone diamine is a compound in which two binary aromatic amine groups are directly bonded to hydrazine. Specifically, the aromatic diamine is a compound in which two binary aromatic amine groups are bonded to the carbon atoms of No. 1 and No. 6 of ruthenium, respectively.
  • Aromatic thiamine is a compound in which a binary aromatic amine group is directly attached to a bend. Specifically, the aromatic guanamine is a compound in which a divalent aromatic amine group is directly bonded to the carbon atom No. 1 of the bend.
  • An aromatic quinone diamine is a compound in which two binary aromatic amine groups are directly bonded to a bend. Specifically, the aromatic quinone diamine is a compound in which two binary aromatic amine groups are bonded to the carbon atoms of No. 1 and No. 6 respectively.
  • the monoamine illuminant based on vinylamine or the singlet illuminant based on arylamine may for example be WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, Singlet emitters in EP 1957606 A1 and US 2008/0113101 A1.
  • the singlet illuminants in the above patent documents can be used as the singlet illuminators of the present embodiment.
  • the singlet illuminant based on the stilbene extreme derivative may, for example, be a singlet illuminant in US Pat. No. 5,121,029 A.
  • the singlet emitter is an indeno-amine or an indeno-diamine, such as the singlet emitter disclosed in WO 2006/122630. Further, the singlet emitter is a benzoindolo-amine or a benzoindolo-diamine, such as the singlet emitter disclosed in WO 2008/006449. Further, the singlet emitter is dibenzoindolo-amine or dibenzoindolo-diamine, such as the singlet emitter disclosed in WO2007/140847.
  • the polycyclic aromatic hydrocarbon compound and its derivative can be used as a material of a singlet illuminant.
  • it may be ⁇ [such as 9,10-di(2-naphthoquinone)], naphthalene, tetraphenyl, xanthene, phenanthrene, anthracene (such as 2,5,8,11-tetra-t-butylhydrazine) , anthracene, phenylene (such as 4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1'-biphenyl), indenylindole, decacycloolefin, hexabenzo Benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886A), arylene vinyl (such as US5121029A, US5130603A), cyclopentadiene (t
  • the singlet emitter is selected from one of the following structural formulae:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex and has the formula M(L)n; wherein M is a metal atom, L is an organic ligand, and L is in one or more positions with G A chemical bond or a coordinate bond is attached; n is an integer greater than one. Further, n is 1, 2, 3, 4, 5 or 6. It should be noted that the compound obtained by coupling a metal complex to a polymer through one or more positions may also function as a triplet emitter.
  • the polymer is an organic ligand.
  • M is a transition metal element, a lanthanide or a lanthanide.
  • M is Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag.
  • M is Os, Ir, Ru, Rh, Re, Pd or Pt.
  • the triplet emitter comprises a chelating ligand.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • the chelating ligand is coordinated to the metal atom through at least two bonding sites.
  • the triplet emitter comprises 2 to 3 identical or different bidentate or multidentate ligands.
  • the organic ligand is a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative or 2 phenylquinoline derivatives.
  • the above organic ligands are all substituted by a substituent.
  • the substituent is, for example, a fluorine-containing methyl group or a trifluoromethyl group.
  • an auxiliary ligand is also included.
  • the ancillary ligand is acetic acid acetone or picric acid.
  • the metal complex that can be used as the triplet emitter has the following structural formula:
  • G is a metal atom
  • Ar 1 ' is a cyclic group containing at least one donor atom (ie, an atom having a lone pair of electrons), and Ar 1 ' is bonded to G through a donor atom
  • Ar 1 ' contains at least one C a cyclic group of an atom
  • Ar 2 ' is bonded to G through a C atom
  • Ar 1 ' and Ar 2 ' are linked by a covalent bond
  • L' is an ancillary ligand
  • m' is 1, 2 or 3
  • n' is 0, 1 or 2.
  • both Ar 1 'and Ar 2 ' may carry one or more substituent groups.
  • the substituent group is oxygen, phenyl or dibenzofuran, and Ar 1 ' and Ar 2 ' can be linked by a substituent group of both.
  • m'Ar 1 ' may be the same group or different groups; m'Ar 2 ' may be the same group or different a group; n'L' may be the same group or a different group.
  • Ar 1 ' is a cyclic group containing at least one donor atom
  • the donor atom is nitrogen or phosphorus
  • n' is 2 or 3. Further, m' is 3.
  • n' is 0 or 1. Further, n' is 0.
  • examples of materials for some triplet emitters and their use can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson Et al.
  • the triplet emitter can be selected from one of the structural formulae in the following table:
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference (ie, ⁇ Est). Specifically, the ⁇ Est of the TADF material is less than 0.3 eV. Further, the ⁇ Est of the TADF material is less than 0.2 eV. Further, the ⁇ Est of the TADF material is less than 0.1 eV. TADF has a good fluorescence quantum efficiency.
  • TADF materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1) , Adachi, et.al.Adv.Mater., 21, 2009, 4802, Adachi, et.al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett., 101, 2012, 093306, Adachi, et. al. Chem.
  • the TADF material can be selected from one of the structural formulae of the following table:
  • one structural formula represents a TADF material, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other meaning.
  • the organic functional material publications for organic functional structural units appearing above are hereby incorporated by reference.
  • the composition of one embodiment includes one of the compound containing a crosslinking group of the above embodiment and the mixture of the above embodiment, and an organic solvent.
  • the organic solvent is at least one selected from the group consisting of an aromatic solvent, an aromatic heteropoly solvent, a ketone solvent, an ether solvent, and an ester solvent. Further, the organic solvent is at least one selected from the group consisting of an aliphatic chain-substituted aromatic solvent, an aliphatic ring-substituted aromatic solvent, an aromatic ketone solvent, and an aromatic ether solvent.
  • the aromatic solvent or the aromatic hetero-solvent is p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-Methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2, 3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-d
  • the ketone solvent is 1-tetralone, 2-tetralone, 2-(phenyl epoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, Benzophenone and derivatives of these compounds, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methyl Phenylacetone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2-nonanone, 3-fluorenone, 5-fluorenone, 2- Anthrone, 2,5-hexanedione, phorone or di-n-pentyl ketone.
  • the ether solvent is 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-di Methoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenethyl ether, 1 , 2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether , 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether,
  • the ester solvent is alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenyl acetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide or oleic acid. Alkyl ester.
  • the ketone solvent is 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, phorone or Di-n-pentyl ketone.
  • the ether solvent is pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, Triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
  • the above composition further comprises another organic solvent.
  • Another organic solvent is selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, and Xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin and hydrazine At least one.
  • the above composition is a solution.
  • the above composition is a suspension.
  • the above composition when the above composition is a solution or a suspension, the above composition may further comprise one of the other components.
  • Other components are used to adjust the viscosity of the solution or suspension, film forming properties or to improve adhesion and the like.
  • the other components may, for example, be surface-active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents or binders.
  • the above composition can be used as an ink for printing.
  • the viscosity and surface tension of the ink are important parameters.
  • a suitable surface tension allows the ink to be adapted to a particular substrate and to a particular printing method.
  • the ink has a surface tension of from 19 dyne/cm to 50 dyne/cm at an operating temperature or at 25 °C. Further, the ink has a surface tension of 22 dyne/cm to 35 dyne/cm at an operating temperature or at 25 °C. Further, the ink has a surface tension of 25 dyne/cm to 33 dyne/cm at an operating temperature or at 25 °C.
  • the viscosity of the ink at an operating temperature or 25 ° C is from 1 cps to 100 cps, and the lower viscosity allows the ink to be suitable for ink jet printing. Further, the viscosity of the ink at an operating temperature or 25 ° C is from 1 cps to 50 cps. Further, the viscosity of the ink at an operating temperature or 25 ° C is in the range of 1.5 cps to 20 cps. Further, the viscosity of the ink at an operating temperature or 25 ° C is from 4.0 cps to 20 cps.
  • the viscosity can be adjusted by different methods, for example, selecting a suitable solvent or a concentration of the functional material in the ink, wherein the functional material is selected from at least one of a compound containing a crosslinking group and an organic functional material.
  • the ink can adjust the concentration of the functional material in the ink according to the printing method used. Specifically, the content of the functional material in the ink is in the range of 0.3% by weight to 30% by weight. Further, the content of the functional material in the ink is from 0.5% by weight to 20% by weight. The content of the functional material in the ink is from 0.5% by weight to 15% by weight. The content of the functional material in the ink is from 0.5% by weight to 10% by weight. The content of the functional material in the ink is from 1% by weight to 5% by weight.
  • the above inks are used to prepare organic electronic devices.
  • the above method of ink for preparing an organic electronic device is printing or coating.
  • printing or coating techniques include, but are not limited to, ink jet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roll printing, torsion roll printing. , lithographic, flexographic, rotary printing, spray coating, brush coating, pad printing, spray printing (Nozzle printing) and slit extrusion coating. Still further, printing or coating techniques include ink jet printing, slit type extrusion coating, jet printing, and gravure printing.
  • a film of an organic functional material according to an embodiment includes the above-mentioned compound containing a crosslinking group.
  • the organic functional material film is prepared by a solution processing method.
  • Organic functional material films can be used in organic electronic devices.
  • a method for preparing an organic functional material film according to an embodiment comprises the following steps (1) to (4):
  • Step (1) preparing a membrane liquid containing the above-mentioned compound containing a crosslinking group.
  • a solution containing the above-mentioned organic component containing a crosslinking group-containing compound is dissolved in a solvent.
  • step (2) the membrane liquid is prepared into a film layer.
  • the above film liquid is applied onto a substrate by a printing or coating method to form a film layer.
  • the printing or coating method may be selected from, but not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twisting. Roll printing, lithography, flexographic printing, rotary printing, spray coating, brushing, pad printing and slit-type extrusion coating.
  • a compound having a crosslinking group in the film layer is subjected to a crosslinking reaction to obtain a cured film.
  • the substrate containing the film layer is subjected to heat treatment at at least 100 ° C to cause a crosslinking reaction of the compound having a crosslinking group in the film layer to obtain a cured film.
  • the film layer may be subjected to ultraviolet light to cause a crosslinking reaction of the compound having a crosslinking group in the film layer to obtain a cured film.
  • Step (4) the cured film is washed with an organic solvent to remove the uncrosslinked solidified compound to obtain an organic functional film. It should be noted that the obtained cured film can meet the actual needs, and the step (4) can be omitted.
  • the thickness of the organic functional film is at least 50% of the thickness of the film layer. Further, the thickness of the organic functional film is at least 60% of the thickness of the film layer. Further, the thickness of the organic functional film is at least 70% of the thickness of the film layer. Further, the thickness of the organic functional film is at least 85% of the thickness of the film layer.
  • the present invention also provides the use of a crosslinking group-containing compound as described above in an organic electronic device.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
  • the organic electronic device is an OLED.
  • the said crosslinking group-containing group The compound is used in a hole transport layer, a hole injection layer or a light-emitting layer of an OLED. Further, the crosslinking group-containing compound is used for a hole transport layer of an OLED.
  • the present invention relates to an organic electronic device comprising at least one compound containing a crosslinking group.
  • the organic electronic device includes a functional layer prepared from the above composition.
  • the organic electronic device comprises at least a cathode, an anode, and a functional layer between the cathode and the anode, and the functional layer contains at least one compound containing a crosslinking group as described above.
  • the organic electronic device is an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic Spintronics, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • organic light emitting field effect transistor an organic light emitting field effect transistor
  • organic laser and an organic Spintronics, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
  • the organic electronic device is an electroluminescent device. Further, as shown in FIG. 1 , the organic electronic device is an OLED 100 (shown in FIG. 1 ), and the OLED 100 includes a substrate 101 , an anode 102 , a light emitting layer 104 , and a cathode 106 . It should be noted that the OLED 100 further includes a hole transport layer 103 and an electron transport layer 105.
  • the substrate 101 is a transparent substrate or an opaque substrate.
  • Transparent substrates can be used to make transparent light-emitting components, see, for example, Bulovic et al. Nature 1996, 380, p29, Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass. Further, the substrate has a smooth surface, and a substrate having no surface defects is a particularly desirable option.
  • the flexible substrate can be a polymeric film or plastic.
  • the glass transition temperature Tg of the substrate 101 is greater than 150 °C. Further, the glass transition temperature Tg of the substrate 101 is greater than 200 °C.
  • the glass transition temperature Tg of the substrate 101 is greater than 250 °C. Further, the glass transition temperature Tg of the substrate 101 is more than 300 °C.
  • suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the anode (102) is a conductive metal, a metal oxide or a conductive polymer.
  • the anode 102 can easily inject holes into a hole injection layer (HIL), a hole transport layer (HTL), or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the anode 102 is laminated on one side of the substrate 101.
  • the absolute value is less than 0.5 eV.
  • the work function of the anode 102 and the absolute value of the difference between the HOMO level or the valence band level of the illuminant 104 in the luminescent layer or the p-type semiconductor material as the HIL or HTL or the electron blocking layer (EBL) is less than 0.3 eV.
  • the work function of the anode 102 and the absolute value of the difference between the HOMO level or the valence band level of the illuminant in the luminescent layer 104 or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.2 eV. .
  • Examples of materials that can be used as the anode 102 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 materials for the anode 102 are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode 102 can be deposited using any suitable technique, such as physical vapor deposition, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode 102 is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • Cathode 106 is a conductive metal or metal oxide.
  • the cathode 106 can easily inject electrons into the EIL, ETL or luminescent layer 104.
  • the cathode 106 is laminated on the side of the anode 102 remote from the substrate 101.
  • the work function of the cathode 106 and the LUMO in the light-emitting layer or the LUMO of the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL)
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the work function of the cathode 106 and the LUMO level or conduction band of the illuminant in the luminescent layer 104 or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL)
  • the absolute value of the difference in energy levels is less than 0.3 eV.
  • the work function of the cathode 106 and the LUMO level or conduction band level of the illuminant in the luminescent layer 104 or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL)
  • the absolute value of the difference is less than 0.2 eV.
  • cathode materials for the devices of the invention.
  • materials that can be used as the cathode 106 include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc.
  • the material capable of functioning as the cathode 106 can be deposited using any suitable technique, such as physical vapor deposition, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the luminescent layer 104 is layered on the side of the anode 102 remote from the substrate 101 and on the side of the cathode 106 adjacent the anode 102.
  • the light-emitting layer 104 is made of the above-described composition containing a crosslinking group. Prepared. Specifically, the light-emitting layer 104 is prepared by printing the above composition.
  • the OLED 100 may further include other functional layers such as a hole injection layer (HIL), a hole transport layer 103 (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), and an electron transport layer 105 ( ETL) or a hole blocking layer (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the hole transport layer 103 is prepared from the above composition containing a crosslinking group.
  • the electron-emitting device has an emission wavelength of 300 nm to 1000 nm. Further, the above-described electron light-emitting device has an emission wavelength of 350 nm to 900 nm. Further, the above-described electron light-emitting device has an emission wavelength of 400 nm to 800 nm.
  • the electronic device is a display device, a lighting device, a light source, or a sensor. It should be noted that the electronic device is not limited to the above device, and may also include other electronic devices.
  • the energy level of the compound is determined by TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. Specifically, use the density function method "Ground State/DFT/Default Spin/B3LYP" and the base group "6-31G(d)" (Charge 0/Spin Singlet) are used to optimize the geometry of the compound.
  • the energy structure of the compound is calculated by the TD-DFT (time-dependent density functional theory) method.
  • SCF/DFT/Default Spin/B3PW91" and base group "6-31G(d)” (Charge 0/Spin Singlet).
  • HOMO and LUMO energy levels are calculated according to the following calibration formulas (1) and (2), S1 and T1 Use directly.
  • HOMO(eV) [(HOMO(G) ⁇ 27.212)-0.9899]/1.1206 calibration formula (1)
  • HOMO(G) is directly calculated by Gaussian 03W, and the unit is Hartree;
  • LUMO(G) is directly calculated by Gaussian 03W, and the unit is Hartree.
  • NPB is a standard material, and the structural formula of NPB is:
  • Example 1 -5.16 -2.17 2.60 3.10
  • Example 2 -5.17 -2.17 2.61 3.15
  • Example 3 -5.14 -2.25 2.47 3.20
  • Example 4 -5.26 -2.19 2.59 3.22
  • Example 5 -5.21 -2.28 2.58 3.20
  • NPB -5.18 -2.34 2.44 3.07
  • the compounds of Examples 1 to 5 have a small difference in energy level between HOMO and LUMO, indicating that the compounds of Examples 1 to 5 have good stability, and at the same time, the ⁇ E ST of the compounds of Examples 1 to 5 [i.e., ⁇ (S 1 -T 1 ), the energy level difference between the singlet energy level and the triplet energy level] is small, indicating that the materials including the compounds of Examples 1 to 5 have high luminous efficiency.
  • the materials of the luminescent layer are as follows:
  • H1 is a co-host material, and its synthesis is referred to the Chinese patent of application number CN201510889328.8;
  • H2 is a co-host material, and its synthesis is referred to the patent WO201034125A1;
  • E1 is a phosphorescent auxiliary material, and its synthesis is referred to the patent CN102668152;
  • the OLED device preparation steps are as follows:
  • ITO transparent electrode (anode) glass substrate cleaning ITO transparent electrode glass substrate was sonicated for 30 minutes using an aqueous solution containing 5% Decon 90 cleaning solution, then ultrasonically cleaned 3 times with deionized water, followed by ultrasonic cleaning with isopropanol 15 minutes, nitrogen drying; treatment under oxygen plasma for 5 minutes to clean the surface of the ITO transparent electrode glass substrate and enhance the work function of the ITO transparent electrode;
  • PEDOT:PSS (Clevios TM PEDOT:PSS Al4083) was spin-coated on an oxygen plasma-treated glass substrate to obtain a film of 80 nm, which was annealed at 150 ° C in air after spin coating. After 20 minutes, the material of the HTL layer was spin-coated on the PEDOT:PSS layer to obtain a 20 nm HTL layer, followed by treatment on a hot plate at 180 ° C for 60 minutes;
  • the materials of the HTL layer were Poly-TFB (CAS: 223569-31-1, available from Lumtec. Corp; 5 mg/mL toluene solution), and the compounds of Examples 1 to 5, respectively.
  • the HTL layer was washed twice with toluene before measuring the thickness of the HTL layer.
  • the current-voltage characteristics and external quantum efficiency of the device were measured by a Keithley 236 current-voltage-measurement system and a calibrated silicon photodiode.
  • the external quantum efficiency of the OLED containing the compounds of Examples 1 to 5 is a relative value of the external quantum efficiency of the OLED containing Poly-TFB. The results are shown in Table 2.
  • the external quantum efficiency of the OLEDs containing the compounds of Examples 1 to 5 was at least 1.43 times the external quantum efficiency of the OLED containing Poly-TFB. It is explained that the compounds of Examples 1 to 5 are more advantageous for improving the performance of the OLED, possibly because the compounds of Examples 1 to 5 contain crosslinkable small molecules, so that these compounds have a higher triplet energy level, thereby having a triplet state. A better blocking effect.

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Abstract

Disclosed is a compound containing a cross-linking group and use thereof. The compound is of structural formula (I); wherein SG is of structural formula (II); Ar is an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms; CLG is a cross-linking group; o is 0 or 1; p is an integer greater than or equal to 2; and A is of structural formula (III). The compound containing a cross-linking group can be used for making an electronic device of a higher efficiency.

Description

含有交联基团的化合物及其应用Compound containing cross-linking group and application thereof 技术领域Technical field
本发明涉及电子领域，特别是涉及一种含有交联基团的化合物及其应用。The present invention relates to the field of electronics, and in particular to a compound containing a crosslinking group and uses thereof.
背景技术Background technique
有机发光二极管(OLEDs，Organic Light-Emitting Diodes)自发明以来(Appl.Phys.Lett.1987,51:913-15.；Nature,1990,347:539-541)，由于有机材料在合成上具有多样性、制造成本相对较低和优良的光学与电学性能，在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力(Chem Rev,2009,109:897-1091；Chem Mater,2011,23:326-340)。Organic Light-Emitting Diodes (OLEDs, Organic Light-Emitting Diodes) since its invention (Appl. Phys. Lett. 1987, 51: 913-15.; Nature, 1990, 347: 539-541), due to the diversity of organic materials in synthesis Sex, relatively low manufacturing costs and excellent optical and electrical properties have great potential for applications in optoelectronic devices such as flat panel displays and lighting (Chem Rev, 2009, 109:897-1091; Chem Mater, 2011, 23:326-340).
OLED器件大多采用多层器件结构，即除了发光层外，还含有一层或多层空穴传输/注入层或电子传输/注入层。因此，除了开发优异的发光材料，开发优异的电子传输/注入材料和空穴传输/注入材料也是实现高性能OLED的关键(J Mater Chem,2008,18:4495-4509.；Acc Chem Res,2005,38:632-643.；Adv Mater,2007,19:810-814)。OLED devices mostly use a multilayer device structure, that is, in addition to the light-emitting layer, one or more layers of hole transport/injection layers or electron transport/injection layers. Therefore, in addition to the development of excellent luminescent materials, the development of excellent electron transport/injection materials and hole transport/injection materials is also the key to achieving high performance OLEDs (J Mater Chem, 2008, 18: 4495-4509.; Acc Chem Res, 2005). , 38: 632-643.; Adv Mater, 2007, 19: 810-814).
对小分子真空蒸镀OLEDs而已，很容易通过真空蒸镀方法获得多层、复杂的高效OLEDs器件，但是由于真空蒸镀方法具有价格昂贵、耗时、浪费材料、难以实现大面积应用等缺点。相比而言，溶液加工型OLEDs由于能够通过低廉的喷墨打印、印刷等溶液加工方法制备大面积、柔性器件等优点，具有广泛的应用前景和商业价值。由于一般有机光电材料具有相似的溶解性，即有机/聚合物发光材料、空穴注入/传输材料、电子注入/传输材料在甲苯、氯仿、氯苯、邻二氯苯、邻二甲苯、四氢呋喃等有机溶剂中具有良好的溶解性，因此在溶液加工方法制备多层、复杂的OLED时，存在界面混溶、界面侵蚀等问题。例如溶液加工聚合物或小分子发光层时，所使用的溶剂会溶解下面的空穴传输层，造成界面混溶、界面侵蚀等问题(J Mater Chem,2008,18:4495-4509.；Chem S℃Rev,2010,39:2500-2521)。For the vacuum evaporation of OLEDs by small molecules, it is easy to obtain multi-layer, complex and high-efficiency OLEDs by vacuum evaporation, but the vacuum evaporation method has the disadvantages of being expensive, time-consuming, wasteful of materials, and difficult to realize large-area applications. In contrast, solution-processed OLEDs have broad application prospects and commercial value because they can produce large-area, flexible devices and the like through low-cost inkjet printing, printing and other solution processing methods. Since general organic photoelectric materials have similar solubility, that is, organic/polymer luminescent materials, hole injection/transport materials, electron injection/transport materials in toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene, tetrahydrofuran, etc. It has good solubility in organic solvents. Therefore, when solution processing methods are used to prepare multilayer and complex OLEDs, there are problems such as interface miscibility and interface corrosion. For example, when a solution is processed into a polymer or a small molecule light-emitting layer, the solvent used dissolves the underlying hole transport layer, causing problems such as interfacial miscibility and interface corrosion (J Mater Chem, 2008, 18: 4495-4509.; Chem S °CRev, 2010, 39: 2500-2521).
采用常规的交联基团如全氟环丁烷基，苯乙烯基，环氧丁烷基，硅酮基，丙烯酸酯基，苯并环丁烯基。修饰共轭聚合物时，聚合物上的交联基团在光照、加热等条件可引发交联基团全氟环丁烷基(Adv.Funct.Mater.,2002,12,745)、苯乙烯基(Adv.Mater.,2007,19,300)、环氧丁烷基(Nature,2003,421,829.)、硅酮基(Acc.Chem.Res.,2005,38,632)，丙烯酸酯基(Chem.Mater.,2003,15,1491)、苯并环丁烷基(Chem.Mater.,2007,19,4827.)发生交联反应，形成不溶不熔的互穿网络聚合物膜，具有优异的抗溶剂性能，可以避免界面混溶、界面侵蚀等问题(TW201406810A,US7592414B2)。Conventional crosslinking groups such as perfluorocyclobutane, styryl, butylene oxide, silicone, acrylate, benzocyclobutenyl are employed. When the conjugated polymer is modified, the crosslinking group on the polymer can initiate a crosslinking group perfluorocyclobutane (Adv. Funct. Mater., 2002, 12, 745) and a styryl group under conditions of light, heat, and the like. Adv. Mater., 2007, 19, 300), butylene oxide (Nature, 2003, 421, 829.), silicone based (Acc. Chem. Res., 2005, 38, 632), acrylate group (Chem. Mater., 2003). , 15, 1491), benzocyclobutane (Chem. Mater., 2007, 19, 4827.) cross-linking reaction, forming an insoluble and infusible interpenetrating network polymer film, with excellent solvent resistance, can Avoid problems such as interface miscibility and interface erosion (TW201406810A, US7592414B2).
但迄今为止报道的可交联高聚物都是基于共轭聚合物。共轭聚合物大多具有较低的三线态能级，会淬灭相邻发光层，如绿光发光层中具有更高三线态能量(相对更短的波长)的激子，同时也不会起到激子阻挡层的作用。这些都制约了OLED器件的性能的提高，不能满足实际需求。However, the crosslinkable polymers reported so far are based on conjugated polymers. Most conjugated polymers have lower triplet energy levels, which quench adjacent luminescent layers, such as excitons with higher triplet energy (relatively shorter wavelengths) in the green luminescent layer, and do not To the role of the exciton blocking layer. These all restrict the improvement of the performance of OLED devices and cannot meet the actual needs.
发明内容Summary of the invention
基于此，有必提供一种能够制作具有较高效率的电子器件的含有交联基团的化合物及其应用。Based on this, it is necessary to provide a compound containing a crosslinking group capable of producing an electronic device having higher efficiency and an application thereof.
一实施方式的含有交联基团的化合物，具有如下结构式(I)：The crosslinking group-containing compound of one embodiment has the following structural formula (I):
Figure PCTCN2017118065-appb-000001
Figure PCTCN2017118065-appb-000001
其中，SG具有结构式(II)：Among them, SG has the structural formula (II):
Figure PCTCN2017118065-appb-000002
Figure PCTCN2017118065-appb-000002
Ar为环原子数为5～20的芳基或环原子数为5～20的杂芳基；Ar is an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms;
CLG为交联基团；CLG is a crosslinking group;
o为0或1； o is 0 or 1;
p为大于或等于2的整数；p is an integer greater than or equal to 2;
A的结构式III为：The structural formula III of A is:
Figure PCTCN2017118065-appb-000003
Figure PCTCN2017118065-appb-000003
其中，R1为F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃基，R2为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基，Wherein R 1 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , a linear alkane having 1 to 10 carbon atoms, and total An alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having 3 to 10 total carbon atoms, and a cycloalkane group having 3 to 10 total carbon atoms; R 2 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms.
-L-为单键或碳原子数为5～40共轭芳基，-L- is a single bond or a conjugated aryl group having 5 to 40 carbon atoms,
Ar1为环原子数为5～40的芳族基或环原子数为5～40的杂芳基，Ar 1 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms.
y为0～5的整数，Y is an integer from 0 to 5,
Ar0选自如下结构式中的一种：Ar 0 is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000004
Figure PCTCN2017118065-appb-000004
其中，Ar2为环原子数为5～40的芳族基或环原子数为5～40的杂芳族基，Wherein Ar 2 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
X为0～4的整数，X1为0～3的整数，X is an integer from 0 to 4, and X1 is an integer from 0 to 3.
-Z-不存在或为单键及二桥联基中的一种，-Z- does not exist or is one of a single bond and a two bridged base,
m选自0～10的整数，m is selected from an integer of 0 to 10,
R9为F、Cl、Br、I、D、CN、NO2、CF3、B(OR14)2、Si(R14)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃，R14为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；R 9 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 14 ) 2 , Si(R 14 ) 3 , a linear alkane having 1 to 10 carbon atoms, and a total carbon atom. The number is from 1 to 10, an alkane ether, an alkane sulfide having a total carbon number of from 1 to 10, a branched alkane having a total carbon number of from 3 to 10, a cycloalkane having a total carbon number of from 3 to 10, and R 14 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
结构式III中的虚线表示L与Ar0连接，结构式(IIIa)中的虚线和圆圈表示L能够与圆圈中两个苯环的任意碳原子或Ar2的结构式中包含的芳香环或杂芳环的任意碳原子连接，结构式(IIIb)及结构式(IIIc)中的虚线均表示L能够连接在虚线穿过的苯环的任意碳原子上。The dotted line in Structural Formula III indicates that L is bonded to Ar 0 , and the dotted line and circle in Structural Formula (IIIa) indicate that L can be bonded to any carbon atom of two benzene rings in the circle or an aromatic ring or heteroaryl ring contained in the structural formula of Ar 2 . Any carbon atom linkage, the dashed lines in structural formula (IIIb) and structural formula (IIIc) all indicate that L can be attached to any carbon atom of the benzene ring through which the dotted line passes.
上述含有交联基团的化合物包含有机功能结构单元和可交联基团，具有好的溶解性和成膜性。该化合物可以通过加热处理或紫外照射，使分子间的可交联基团发生交联反应，从而使该化合物固化形成薄膜。同时，由于上述化合物具有较好的溶解性和成膜性，使得含有该化合物的组合物具有较好的印刷性及成膜性能，进而使得含有该化合物或该组合物的电子器件具有较高的性能，最终使得电子器件的制造成本低、效率高。The above-mentioned compound containing a crosslinking group contains an organic functional structural unit and a crosslinkable group, and has good solubility and film formability. The compound can be crosslinked by heat treatment or ultraviolet irradiation to crosslink the intermolecular crosslinkable groups, thereby curing the compound to form a film. At the same time, since the above compound has good solubility and film forming property, the composition containing the compound has good printability and film-forming property, thereby making the electronic device containing the compound or the composition high. The performance ultimately makes the manufacturing cost of the electronic device low and efficient.
附图说明DRAWINGS
图1为一实施方式的有机发光二极管的结构示意图。FIG. 1 is a schematic structural view of an organic light emitting diode according to an embodiment.
具体实施方式detailed description
为了便于理解本发明，下面对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技 术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein and techniques pertaining to the technical field of the invention The surgeon usually understands the same meaning. The terminology used in the description of the present invention is for the purpose of describing particular embodiments and is not intended to limit the invention.
以下实施方式中，如未特别说明，芳基指至少包含一个芳环的烃基，包括单环芳基和多环芳基。多环芳基也可以为稠芳基，即具有两个或多个环的芳基，且其中相邻两个环共用两个碳原子(即稠环)。芳基例如可以是苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、螺芴或其衍生物。需要说明的是，芳基中的H被取代基取代时，在本实施方式中也认为是芳基。In the following embodiments, the aryl group means a hydrocarbon group containing at least one aromatic ring, including a monocyclic aryl group and a polycyclic aryl group, unless otherwise specified. The polycyclic aryl group may also be a fused aryl group, that is, an aryl group having two or more rings, and wherein two adjacent rings share two carbon atoms (ie, a fused ring). The aryl group may be, for example, benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzofluorene, triphenylene, anthracene, anthracene, snail or a derivative thereof. In the case where H in the aryl group is substituted by a substituent, it is also considered to be an aryl group in the present embodiment.
杂芳基指包含至少一个杂原子的芳族基基，包括单环杂芳基和多环杂芳基。其中，杂原子例如可以选自Si、P、O、N、S及Ge中的至少一种；进一步地，杂原子选自Si、P、O、N及S中的至少一种；更进一步地，杂原子选自O、N及S中的至少一种。多环杂芳基也可以为稠杂芳基，即包含至少一个杂原子的稠芳基。杂芳基例如可以是呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、吡咯、吡唑、***、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮或其衍生物。需要说明的是，杂芳基中的H被取代基取代时，在本实施方式中也认为是杂芳基。Heteroaryl refers to an aromatic radical containing at least one heteroatom, including monocyclic heteroaryl and polycyclic heteroaryl. Wherein the hetero atom may be, for example, at least one selected from the group consisting of Si, P, O, N, S, and Ge; further, the hetero atom is selected from at least one of Si, P, O, N, and S; The hetero atom is selected from at least one of O, N and S. The polycyclic heteroaryl group may also be a heteroaromatic group, that is, a fused aryl group containing at least one hetero atom. The heteroaryl group may, for example, be furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, Anthracene, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine , pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone or a derivative thereof. In addition, when H in a heteroaryl group is substituted by a substituent, it is also considered to be a heteroaryl group in this embodiment.
需要说明的是，芳基或杂芳基还可以包括至少两个芳环或杂芳环被非芳环基连接而构成的基团，其中，非芳环基中的非H原子的数量小于10％。在其中一个实施方式中，非芳环基中的非H原子的数量小于5％。在其中一个实施方式中，非芳环基为C原子、N原子或O原子。It should be noted that the aryl or heteroaryl group may further include a group in which at least two aromatic rings or heteroaromatic rings are bonded by a non-aromatic ring group, wherein the number of non-H atoms in the non-aromatic ring group is less than 10 %. In one embodiment, the number of non-H atoms in the non-aromatic ring group is less than 5%. In one embodiment, the non-aromatic ring group is a C atom, an N atom or an O atom.
一实施方式的含有交联基团的化合物，具有如下结构式(I)：The crosslinking group-containing compound of one embodiment has the following structural formula (I):
Figure PCTCN2017118065-appb-000005
Figure PCTCN2017118065-appb-000005
其中，SG具有结构式(II)：Among them, SG has the structural formula (II):
Figure PCTCN2017118065-appb-000006
Figure PCTCN2017118065-appb-000006
Ar为环原子数为5～20的芳基或环原子数为5～20的杂芳基；Ar is an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms;
CLG为交联基团；CLG is a crosslinking group;
o为0或1；o is 0 or 1;
p为大于或等于2的整数；p is an integer greater than or equal to 2;
A的结构式III为：The structural formula III of A is:
Figure PCTCN2017118065-appb-000007
Figure PCTCN2017118065-appb-000007
其中，R1为F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃R2为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基，Wherein R 1 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , a linear alkane having 1 to 10 carbon atoms, and total An alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having 3 to 10 total carbon atoms, and a cycloalkane R 2 having 3 to 10 total carbon atoms. And H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
-L-为单键或碳原子数为5～40共轭芳基，-L- is a single bond or a conjugated aryl group having 5 to 40 carbon atoms,
Ar1为环原子数为5～40的芳族基团或环原子数为5～40的杂芳族基团，Ar 1 is an aromatic group having 5 to 40 ring atoms or a heteroaromatic group having 5 to 40 ring atoms.
y为0～5的整数，Y is an integer from 0 to 5,
Ar0选自如下结构式中的一种： Ar 0 is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000008
Figure PCTCN2017118065-appb-000008
其中，Ar2为环原子数为5～40的芳族基或环原子数为5～40的杂芳族基，Wherein Ar 2 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
X为0～4的整数，X1为0～3的整数，X is an integer from 0 to 4, and X1 is an integer from 0 to 3.
-Z-不存在或为单键及二桥联基中的一种，-Z- does not exist or is one of a single bond and a two bridged base,
m选自0～10的整数，m is selected from an integer of 0 to 10,
R9为F、Cl、Br、I、D、CN、NO2、CF3、B(OR14)2、Si(R14)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃，每一个基团均可被一个或多个活性基团R14取代，且一个或多个非相邻的亚甲基(CH2)可以被以下基团替换，它们包含R14C＝CR14、C＝C、Si(R14)2、Ge(R14)2、Sn(R14)2、C＝O、C＝S、C＝Se、C＝N(R14)、O、S、-COO-、或CONR14，其中一个或多个H原子可被D、F、Cl、Br、I、CN、N2、活性基团R14取代的芳香胺、芳基取代的芳香胺、杂芳基取代的芳香胺替换、取代或未被取代的咔唑替换。R14为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基。需要说明的是，结构式III中的虚线表示L与Ar0连接，结构式(IIIa)中的虚线和圆圈表示所述L能够与圆圈中两个苯环的任意碳原子或Ar2的结构式中包含的芳香环或杂芳环的任意碳原子连接，结构式(IIIb)及结构式(IIIc)中的虚线均表示L能够连接在虚线穿过的苯环的任意碳原子上。R 9 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 14 ) 2 , Si(R 14 ) 3 , a linear alkane having 1 to 10 carbon atoms, and a total carbon atom. Alkane ether having a number of 1 to 10, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and a cycloalkane having a total carbon number of 3 to 10, each of which is a base. The group may be substituted by one or more reactive groups R 14 and one or more non-adjacent methylene groups (CH 2 ) may be replaced by the group consisting of R 14 C=CR 14 , C=C , Si(R 14 ) 2 , Ge(R 14 ) 2 , Sn(R 14 ) 2 , C=O, C=S, C=Se, C=N(R 14 ), O, S, -COO-, Or CONR 14 , wherein one or more H atoms may be substituted by an aromatic amine substituted with D, F, Cl, Br, I, CN, N 2 , a reactive group R 14 , an aryl-substituted aromatic amine, a heteroaryl group Amine substituted, substituted or unsubstituted carbazole replacement. R 14 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms. It should be noted that the dotted line in the structural formula III indicates that L is bonded to Ar 0 , and the dotted line and the circle in the structural formula (IIIa) indicate that the L can be combined with any carbon atom of the two benzene rings in the circle or the structural formula of Ar 2 . Any carbon atom of the aromatic or heteroaromatic ring is bonded, and the dotted lines in the structural formula (IIIb) and the structural formula (IIIc) each indicate that L can be attached to any carbon atom of the benzene ring through which the dotted line passes.
在其中一个实施例中，Ar为环原子数为6～20的芳基或环原子数为6～20的杂芳基。进一步地，Ar为环原子数为6～16的芳基或环原子数为6～16的杂芳基。更进一步地，Ar为环原子数为6～12的芳基或环原子数为6～12的杂芳基。In one embodiment, Ar is an aryl group having 6 to 20 ring atoms or a heteroaryl group having 6 to 20 ring atoms. Further, Ar is an aryl group having 6 to 16 ring atoms or a heteroaryl group having 6 to 16 ring atoms. Further, Ar is an aryl group having 6 to 12 ring atoms or a heteroaryl group having 6 to 12 ring atoms.
在其中一个实施例中，Ar为环原子数为6～20的取代的芳基或环原子数为6～20的取代的杂芳基。进一步地，Ar为环原子数为6～16的取代的芳基或环原子数为6～16的取代的杂芳基。更进一步地，Ar为环原子数为6～12的取代的芳基或环原子数为6～12的取代的杂芳基。In one embodiment, Ar is a substituted aryl group having 6 to 20 ring atoms or a substituted heteroaryl group having 6 to 20 ring atoms. Further, Ar is a substituted aryl group having 6 to 16 ring atoms or a substituted heteroaryl group having 6 to 16 ring atoms. Further, Ar is a substituted aryl group having 6 to 12 ring atoms or a substituted heteroaryl group having 6 to 12 ring atoms.
在其中一个实施例中，Ar为环原子数为5～18的芳基或环原子数为5～18的杂芳基。进一步地，Ar为环原子数为5～15的芳基或环原子数为5～15的杂芳基。更进一步地，Ar为环原子数为5～18的芳基或环原子数为5～15的杂芳基。In one embodiment, Ar is an aryl group having 5 to 18 ring atoms or a heteroaryl group having 5 to 18 ring atoms. Further, Ar is an aryl group having 5 to 15 ring atoms or a heteroaryl group having 5 to 15 ring atoms. Further, Ar is an aryl group having 5 to 18 ring atoms or a heteroaryl group having 5 to 15 ring atoms.
在其中一个实施例中，Ar为环原子数为5～18的取代的芳基或环原子数为5～18的取代的杂芳基。进一步地，Ar为环原子数为5～15的取代的芳基或环原子数为5～15的取代的杂芳基。更进一步地，Ar为环原子数为5～18的取代的芳基或环原子数为5～15的取代的杂芳基。In one embodiment, Ar is a substituted aryl group having 5 to 18 ring atoms or a substituted heteroaryl group having 5 to 18 ring atoms. Further, Ar is a substituted aryl group having 5 to 15 ring atoms or a substituted heteroaryl group having 5 to 15 ring atoms. Further, Ar is a substituted aryl group having 5 to 18 ring atoms or a substituted heteroaryl group having 5 to 15 ring atoms.
在其中一个实施例中，Ar选自苯、联苯、三苯基、苯并、芴、吲哚芴及其衍生物中的一种。In one embodiment, Ar is selected from the group consisting of benzene, biphenyl, triphenyl, benzo, anthracene, anthracene, and derivatives thereof.
在其中一个实施例中，Ar选自三苯胺、二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯并联吡啶、吡唑、咪唑、***类、恶唑、噻唑、恶二唑、恶***、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪，恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、苯异恶唑、二苯并恶唑、异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃并吡啶、二吡啶并呋喃、苯并噻吩并吡啶、二吡啶并噻吩、苯并硒吩并吡啶及二吡啶并硒吩中的一种。In one embodiment, Ar is selected from the group consisting of triphenylamine, dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, anthracene Carbazole, pyridinium, pyrrole parallel pyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyridyl Oxazine, triazine, oxazine, oxazine, oxadiazine, hydrazine, benzimidazole, oxazole, benzoxazole, dibenzoxazole, isoxazole, benzothiazole, quinoline, iso Quinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, dipyridine One of furan, benzothienopyridine, dipyridothiophene, benzoselenopyridine, and dipyridopene.
在其中一个实施例中，Ar选自如下结构式中的一种： In one embodiment, Ar is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000009
Figure PCTCN2017118065-appb-000009
其中，X2为C-R15或N，Where X 2 is CR 15 or N,
Y2为C-R16-R17、Si-R18-R19、N-R20、C(＝O)、S(＝O)2、O或S，Y 2 is CR 16 -R 17 , Si-R 18 -R 19 , NR 20 , C(=O), S(=O) 2, O or S,
-R15、-R16、-R17、-R18、-R19及-R20分别独立选自为H、D、F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠环芳基、碳原子数为4～60的稠杂环芳基及上述基团中至少两个相互连接形成的组合基团中的一种。-R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each independently selected from the group consisting of H, D, F, -CN, -NO 2 , -CF 3 , alkenyl, alkynyl , an amine group, an acyl group, an amide group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, carbon An aryl group having 6 to 60 atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused ring aryl group having 7 to 60 carbon atoms, a fused heterocyclic aryl group having 4 to 60 carbon atoms, and the above One of the combination groups formed by at least two interconnections in the group.
在其中一个实施方式中，-R15、-R16、-R17、-R18、-R19及-R20均能够自身形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a single ring. Aryl or polycyclic aryl.
在其中一个实施方式中，-R15能够分别与-R16、-R17、-R18、-R19及-R20形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 15 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 16 , -R 17 , -R 18 , -R 19 and -R 20 , respectively. Aryl or polycyclic aryl.
在其中一个实施方式中，-R20能够分别与-R16、-R17、-R18、-R19及-R15形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 20 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 16 , -R 17 , -R 18 , -R 19 and -R 15 , respectively. Aryl or polycyclic aryl.
在其中一个实施方式中，-R16和-R17之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 16 and -R 17 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
在其中一个实施方式中，-R18和-R19之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 18 and -R 19 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
在其中一个实施例中，-R15、-R16、-R17、-R18、-R19及-R20分别独立选自为碳原子数1～60的取代的烷基、碳原子数为3～60的取代的环烷基、碳原子数为6～60的取代的芳基、碳原子数为3～60的取代的杂芳基、碳原子数为7～60的取代的稠环芳基、碳原子数为4～60的取代的稠杂环芳基。In one embodiment, -R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each independently selected from substituted alkyl groups having 1 to 60 carbon atoms, and carbon atoms. a substituted cycloalkyl group of 3 to 60, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, or a substituted fused ring having 7 to 60 carbon atoms. An aryl group or a substituted fused heterocyclic aryl group having 4 to 60 carbon atoms.
在其中一个实施例中，CLG为环状单烯基、线状单烯基、线状二烯基、炔基、烯氧基、二烯氧基、丙烯酸基、环氧丙烷基、环氧乙烷基、硅烷基或环丁烷基。CLG使得含有交联基团的化合物能够发生交联反应，进而增加含有交联基团化合物的抗溶剂性。具体地，CLG能 够在至少100℃、隔绝水和氧气的环境下，使含有交联基团的化合物之间通过CLG发生交联反应。在其中一个实施例中，上述交联反应可通过光照得到增强。进一步地，上述交联反应可通过UV光照(即紫外光照)得到增强。In one embodiment, the CLG is a cyclic monoalkenyl group, a linear monoalkenyl group, a linear dienyl group, an alkynyl group, an alkenyloxy group, a dienyloxy group, an acrylic group, an oxypropylene group, an epoxy group Alkyl, silane or cyclobutane. CLG enables a compound containing a crosslinking group to undergo a crosslinking reaction, thereby increasing the solvent resistance of the compound containing a crosslinking group. Specifically, CLG can It is sufficient to crosslink the CL-containing compound between the compounds containing a crosslinking group in an environment of at least 100 ° C, water and oxygen. In one of the embodiments, the above crosslinking reaction can be enhanced by illumination. Further, the above crosslinking reaction can be enhanced by UV light (i.e., ultraviolet light).
在其中一个实施例中，CLG选自如下基团中的一种：In one embodiment, the CLG is selected from one of the following groups:
Figure PCTCN2017118065-appb-000010
Figure PCTCN2017118065-appb-000010
Figure PCTCN2017118065-appb-000011
Figure PCTCN2017118065-appb-000011
其中，R10、R11、R12及R13分别独立选自F、Cl、Br、I、D、CN、NO2、CF3、B(OR21)2、Si(R21)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃中的一种，R21为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；Wherein R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 21 ) 2 , Si(R 21 ) 3 , carbon a linear alkane having 1 to 10 atoms, an alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and total One of the cycloalkanes having 3 to 10 carbon atoms, R 21 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a ring atom number 5 to 10 heteroaryl groups;
Ar12为环原子数为5～40的芳族基或环原子数为5～40的杂芳基；Ar 12 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
s为大于等于0的整数，t为大于等于0的整数；s is an integer greater than or equal to 0, and t is an integer greater than or equal to 0;
上述结构式中的虚线表示CLG与其他基团的连接。The dotted line in the above structural formula indicates the connection of the CLG to other groups.
在其中一个实施例中，o为0。In one of the embodiments, o is zero.
在其中一个实施例中，o为1。In one of the embodiments, o is one.
在其中一个实施例中，p为2～20的整数。进一步地，p为2～10的整数。进一步地，p为2～8的整数。进一步地，p为2～5的整数。进一步地，p为3～4的整数。In one embodiment, p is an integer from 2 to 20. Further, p is an integer of 2 to 10. Further, p is an integer of 2-8. Further, p is an integer of 2 to 5. Further, p is an integer of 3 to 4.
在其中一个实施例中，-L-为连接基团、单键或碳原子数为5～40的共轭芳基。In one embodiment, -L- is a linking group, a single bond or a conjugated aryl group having 5 to 40 carbon atoms.
进一步地，L为碳原子数为5～40的被R22取代的共轭芳基，R22为F、Cl、Br、I、D、CN、NO2、CF3、B(OR23)2、Si(R23)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃，每一个基团均可被一个或多个活性基团R23取代，且一个或多个非相邻的亚甲基(CH2)可以被以下基团替换，它们包含R14C＝CR14、C＝C、Si(R23)2、Ge(R23)2、Sn(R23)2、C＝O、C＝S、C＝Se、C＝N(R23)、O、S、-COO-、或CONR23，其中一个或多个H原子可被D、F、Cl、Br、I、CN、N2、活性基团R14取代的芳香胺、芳基取代的芳香胺、杂芳基取代的芳香胺替换、取代或未被取代的咔唑替换。R23为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基。Further, L is a conjugated aryl group substituted with R 22 having 5 to 40 carbon atoms, and R 22 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 23 ) 2 , Si(R 23 ) 3 , a linear alkane having 1 to 10 carbon atoms, an alkane ether having 1 to 10 total carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, and a total carbon number of 3 to 10 branched alkane, a cycloalkane having 3 to 10 total carbon atoms, each of which may be substituted by one or more reactive groups R 23 and one or more non-adjacent methylene groups (CH 2 ) may be replaced by a group comprising R 14 C=CR 14 , C=C, Si(R 23 ) 2 , Ge(R 23 ) 2 , Sn(R 23 ) 2 , C=O, C =S, C=Se, C=N(R 23 ), O, S, -COO-, or CONR 23 , wherein one or more H atoms can be D, F, Cl, Br, I, CN, N 2 The reactive group R 14 substituted aromatic amine, aryl substituted aromatic amine, heteroaryl substituted aromatic amine substituted, substituted or unsubstituted carbazole is substituted. R 23 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms.
在其中一个实施例中，L为具有一个苯环的连接基团。In one embodiment, L is a linking group having a phenyl ring.
进一步地，L的结构式选自如下结构式的一种：Further, the structural formula of L is selected from one of the following structural formulas:
Figure PCTCN2017118065-appb-000012
Figure PCTCN2017118065-appb-000012
其中，R25为F、Cl、Br、I、D、CN、NO2、CF3、B(OR24)2、Si(R24)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃，每一个基团均可被一个或多个活性基团R24取代，且一个或多个非相邻的亚甲基(CH2)可以被以下基团替换，它们包含R24C＝CR24、C＝C、Si(R24)2、Ge(R24)2、Sn(R24)2、C＝O、C＝S、C＝Se、C＝N(R24)、O、S、-COO-、或CONR24，其中一个或多个H原子可被D、F、Cl、Br、I、CN、N2、活性基团R14取代的芳香胺、芳基取代的芳香胺、杂芳基取代的芳香胺替换、取代或未被取代的咔唑替换。R24为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；Wherein R 25 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 24 ) 2 , Si(R 24 ) 3 , a linear alkane having 1 to 10 carbon atoms, and total An alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having 3 to 10 total carbon atoms, and a cycloalkane having 3 to 10 total carbon atoms, each One group may be substituted by one or more reactive groups R 24 and one or more non-adjacent methylene groups (CH 2 ) may be replaced by the group comprising R 24 C=CR 24 , C =C, Si(R 24 ) 2 , Ge(R 24 ) 2 , Sn(R 24 ) 2 , C=O, C=S, C=Se, C=N(R 24 ), O, S, -COO -, or CONR 24 , an aromatic amine in which one or more H atoms may be substituted by D, F, Cl, Br, I, CN, N 2 , a reactive group R 14 , an aryl-substituted aromatic amine, a heteroaryl group Substituted aromatic amine replacement, substituted or unsubstituted carbazole replacement. R 24 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
x3为0～4的整数； X3 is an integer from 0 to 4;
上述结构式中的虚线表示L与其他基团的连接。The dotted line in the above structural formula indicates the connection of L to other groups.
在其中一个实施例中，Ar1及Ar2分别独立选自环原子数为6～40的芳基或环原子数为6～30的杂芳基。进一步地，Ar1及Ar2分别独立选自环原子数为6～30的芳基或环原子数为6～30的杂芳基。进一步地，L、Ar1及Ar2分别独立选自环原子数为6～25的芳基或环原子数为6～25的杂芳基。In one embodiment, Ar 1 and Ar 2 are each independently selected from an aryl group having 6 to 40 ring atoms or a heteroaryl group having 6 to 30 ring atoms. Further, Ar 1 and Ar 2 are each independently selected from an aryl group having 6 to 30 ring atoms or a heteroaryl group having 6 to 30 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 6 to 25 ring atoms or a heteroaryl group having 6 to 25 ring atoms.
在其中一个实施例中，L、Ar1及Ar2分别独立选自环原子数为5～40的芳基或环原子数为5～40的杂芳基。进一步地，L、Ar1及Ar2分别独立选自环原子数为5～30的芳基或环原子数为5～30的杂芳基。进一步地，L、Ar1及Ar2分别独立选自环原子数为5～20的芳基或环原子数为5～20的杂芳基。进一步地，L、Ar1及Ar2分别独立选自环原子数为5～15的芳基或环原子数为5～15的杂芳基。In one embodiment, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 30 ring atoms or a heteroaryl group having 5 to 30 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms. Further, L, Ar 1 and Ar 2 are each independently selected from an aryl group having 5 to 15 ring atoms or a heteroaryl group having 5 to 15 ring atoms.
在其中一个实施例中，上述芳基包含6～15个碳原子。进一步地，上述芳基包含6～10个碳原子。进一步地，上述杂芳基包含2～15个碳原子。更进一步地，上述杂芳基包含2～10个碳原子和至少一个杂原子，条件是碳原子和杂原子的总数至少为4。In one embodiment, the above aryl group contains 6 to 15 carbon atoms. Further, the above aryl group contains 6 to 10 carbon atoms. Further, the above heteroaryl group contains 2 to 15 carbon atoms. Further, the above heteroaryl group contains 2 to 10 carbon atoms and at least one hetero atom, provided that the total number of carbon atoms and hetero atoms is at least 4.
在其中一个实施例中，L、Ar1及Ar2分别独立选自如下基团的一种：In one embodiment, L, Ar 1 and Ar 2 are each independently selected from one of the following groups:
Figure PCTCN2017118065-appb-000013
Figure PCTCN2017118065-appb-000013
其中，X5为C-R30或N，Where X 5 is CR 30 or N,
Y5为C-R31-R32、Si-R33-R34、N-R35、C(＝O)、S(＝O)2、O或S，Y 5 is CR 31 -R 32 , Si-R 33 -R 34 , NR 35 , C(=O), S(=O) 2, O or S,
-R30、-R31、-R32、-R33、-R34及-R35分别独立选自为H、D、F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠环芳基、碳原子数为4～60的稠杂环芳基及上述基团中至少两个相互连接形成的组合基团中的一种。-R 30 , -R 31 , -R 32 , -R 33 , -R 34 and -R 35 are each independently selected from the group consisting of H, D, F, -CN, -NO 2 , -CF 3 , alkenyl, alkynyl , an amine group, an acyl group, an amide group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, carbon An aryl group having 6 to 60 atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused ring aryl group having 7 to 60 carbon atoms, a fused heterocyclic aryl group having 4 to 60 carbon atoms, and the above One of the combination groups formed by at least two interconnections in the group.
在其中一个实施方式中，-R30、-R31、-R32、-R33、-R34及-R35均能够自身形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 30 , -R 31 , -R 32 , -R 33 , -R 34 and -R 35 are each capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a single ring. Aryl or polycyclic aryl.
在其中一个实施方式中，-R35能够分别与-R30、-R31、-R32、-R33及-R34形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 35 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 30 , -R 31 , -R 32 , -R 33 and -R 34 , respectively. Aryl or polycyclic aryl.
在其中一个实施方式中，-R20能够分别与-R16、-R17、-R18、-R19及-R15形成单环脂族环 基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 20 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic ring with -R 16 , -R 17 , -R 18 , -R 19 and -R 15 , respectively. Aryl or polycyclic aryl.
在其中一个实施方式中，-R31和-R32之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 31 and -R 32 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
在其中一个实施方式中，-R33和-R34之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, -R 33 and -R 34 are capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
在其中一个实施例中，-R30、-R31、-R32、-R33、-R34及-R35分别独立选自为碳原子数1～60的取代的烷基、碳原子数为3～60的取代的环烷基、碳原子数为6～60的取代的芳基、碳原子数为3～60的取代的杂芳基、碳原子数为7～60的取代的稠环芳基、碳原子数为4～60的取代的稠杂环芳基中的一种。In one embodiment, -R 30 , -R 31 , -R 32 , -R 33 , -R 34 and -R 35 are each independently selected from substituted alkyl groups having 1 to 60 carbon atoms, and carbon atoms. a substituted cycloalkyl group of 3 to 60, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, or a substituted fused ring having 7 to 60 carbon atoms. An aryl group or one of the substituted fused heterocyclic aryl groups having 4 to 60 carbon atoms.
在其中一个实施例中，L、Ar1及Ar2分别独立选自如下结构式的一种：In one embodiment, L, Ar 1 and Ar 2 are each independently selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000014
Figure PCTCN2017118065-appb-000014
Figure PCTCN2017118065-appb-000015
Figure PCTCN2017118065-appb-000015
其中，上述结构式下面的编号(如C36)仅代表相应结构式的序号，不具有其他含义，上述结构式中，一个结构式代表一种物质，相邻结构式之间的交错仅是文档排版问题，不具有其他意义；Wherein, the number below the structural formula (such as C36) only represents the serial number of the corresponding structural formula, and has no other meanings. In the above structural formula, one structural formula represents a substance, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other significance;
-R3选自-H、-F、-Cl、-Br、-I、-D、-CN、-NO2、-CF3、B(OR40)2、Si(R40)3、直链烷烃、烷烃醚、碳原子数为1～10的烷烃硫醚、支链烷烃、环烷烃碳原子数为6～10的芳基中的一种，R40为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；-R 3 is selected from -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , B(OR 40 ) 2 , Si(R 40 ) 3 , linear An alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, or an aryl group having a cycloalkane having 6 to 10 carbon atoms, and R 40 is H, D, and having 1 carbon atom. a fatty alkane group of ～10, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
u选自0～2的整数中的一个，v选自0～3的整数中的一个，w选自0～4的整数中的一个，t选自0～5的整数中的一个；u is selected from one of integers from 0 to 2, v is selected from one of integers from 0 to 3, w is selected from one of integers from 0 to 4, and t is selected from one of integers from 0 to 5;
上述结构式中的虚线表示该结构式与其他基团的连接。The dotted line in the above structural formula indicates the connection of the structural formula to other groups.
在其中一个实施例中，Z不存在，且A的结构式为：In one of the embodiments, Z does not exist and the structural formula of A is:
Figure PCTCN2017118065-appb-000016
Figure PCTCN2017118065-appb-000016
其中，X4选自0～5的整数中的一个，其他的符号与上述指出的意义相同。Wherein X4 is selected from one of integers from 0 to 5, and the other symbols have the same meanings as indicated above.
在其中一个实施例中，Z为二桥联基时，-Z-为如下结构式中的一种：In one embodiment, when Z is a two bridging group, -Z- is one of the following structural formulas:
Figure PCTCN2017118065-appb-000017
Figure PCTCN2017118065-appb-000017
Figure PCTCN2017118065-appb-000018
Figure PCTCN2017118065-appb-000018
其中，R4、R5、R6与R7分别独立选自F、Cl、Br、I、D、CN、NO2、CF3、B(OR25)2、Si(R25)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃的基团中的一种，R25为H、D、碳原子数为1～10的脂肪族烷烃基、芳香碳氢化合物基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；上述基团中的虚线表示Z能够与Ar0结构式I中两个苯环连接。Wherein R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 25 ) 2 , Si(R 25 ) 3 , carbon a linear alkane having 1 to 10 atoms, an alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and total One of the groups of a cycloalkane having 3 to 10 carbon atoms, R 25 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aromatic hydrocarbon group, and a ring number of 5 to 5 An aryl group having 10 or a heteroaryl group having 5 to 10 ring atoms; a broken line in the above group indicates that Z can be bonded to two benzene rings in the structural formula I of Ar 0 .
在其中一个实施方式中，A的结构式选自如下结构的一种：In one embodiment, the structural formula of A is selected from one of the following structures:
Figure PCTCN2017118065-appb-000019
Figure PCTCN2017118065-appb-000019
Figure PCTCN2017118065-appb-000020
Figure PCTCN2017118065-appb-000021
上述结构式中，一个结构式代表一种A，相邻结构式之间的交错仅是文档排版问题，不具有其他意义。
Figure PCTCN2017118065-appb-000020
Figure PCTCN2017118065-appb-000021
In the above structural formula, one structural formula represents an A, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other meaning.
在其中一个实施例中，SG选自如下结构式中的一种：In one embodiment, the SG is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000022
Figure PCTCN2017118065-appb-000022
Figure PCTCN2017118065-appb-000023
Figure PCTCN2017118065-appb-000023
其中，R8选自碳原子数为1～20的直链烷基、碳原子数为1～20的烷氧基、碳原子数为1～20的硫代烷氧基、碳原子数为3～20的支链烷基、碳原子数为3～20的环状烷基、碳原子数为3～20的烷氧基、碳原子数为3～20的硫代烷氧基、碳原子数为3～20的甲硅烷基、碳原子数为1～20的酮基、碳原子数为2～20的烷氧基羰基、碳原子数为7～20的芳氧基羰基、氰基基团(-CN)、氨基甲酰基(-C(＝O)NH2)、卤甲酰基(-C(＝O)-X，其中X代表卤素原子)、甲酰基(-C(＝O)-H)、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、硝基、CF3、Cl、Br、F、可交联的基团、碳原子数为5～40的芳基、碳原子数为5～40的杂芳基、碳原子数为5～40的芳氧基、碳原子数为5～40的杂芳氧基及上述基团中至少两个相互连接形成的组合基团中的一种；Wherein R 8 is selected from a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms; a branched alkyl group of ～20, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a thioalkoxy group having 3 to 20 carbon atoms, and a carbon number a silyl group of 3 to 20, a ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, and a cyano group. (-CN), carbamoyl (-C(=O)NH 2 ), haloformyl (-C(=O)-X, wherein X represents a halogen atom), formyl (-C(=O)-H ), isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF 3 , Cl, Br, F, crosslinkable group, carbon number 5 to 40 An aryl group, a heteroaryl group having 5 to 40 carbon atoms, an aryloxy group having 5 to 40 carbon atoms, a heteroaryloxy group having 5 to 40 carbon atoms, and at least two of the above groups are bonded to each other One of the combined groups formed;
n为大于0的整数；n is an integer greater than 0;
-L1-表示单键或连接基团；-L 1 - represents a single bond or a linking group;
上述结构式中的虚线表示SG与其他基团的连接。The dotted line in the above structural formula indicates the connection of SG to other groups.
在其中一个实施例中，R8能够自身形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。In one embodiment, R 8 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group by itself.
在其中一个实施例中，R8为碳原子数为1～20的直链烷基、碳原子数为1～20的烷氧基、碳原子数为3～20的支链烷基或碳原子数为3～20烷氧基。In one embodiment, R 8 is a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms or a carbon atom. The number is 3 to 20 alkoxy groups.
在其中一个实施例中，L1为芳基或杂芳基。在其中一个实施例中，L1选自如下结构式中的一种：In one embodiment, L 1 is aryl or heteroaryl. In one embodiment, L 1 is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000024
Figure PCTCN2017118065-appb-000024
Figure PCTCN2017118065-appb-000025
Figure PCTCN2017118065-appb-000025
上述结构式中的虚线表示该结构式与其他基团的连接。The dotted line in the above structural formula indicates the connection of the structural formula to other groups.
在其中一个实施例中，结构式I中的单独的H原子或CH2基团可被L1取代.In one embodiment, the individual H atom or CH 2 group of formula I can be substituted with L 1 .
在其中一个实施例中，结构式I中的单独的H原子或CH2基团可被R41取代，R41为具有1～40个C原子的烷基。其中，R41选自以下的基团中的一种：甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，环己烯基，庚烯基，环庚烯基，辛烯基，环辛烯基，乙炔基，丙炔基，丁炔基，戊炔基，己炔基和辛炔基。进一步地，具有1～40个C原子的烷氧基为甲氧基，三氟甲氧基，乙氧基，正丙氧基，异丙氧基，正丁氧基，异丁氧基，仲丁氧基，叔丁氧基或甲基丁氧基。In one embodiment, a single H atom in the structural formula I or CH 2 groups may be substituted with R 41, R 41 is an alkyl group having 1 to 40 C atoms. Wherein R 41 is selected from one of the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclo Butyl, methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl , pentafluoroethyl, trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octene Base, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl. Further, the alkoxy group having 1 to 40 C atoms is a methoxy group, a trifluoromethoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, or a secondary group. Butoxy, tert-butoxy or methylbutoxy.
在其中一个实施例中，上述含有交联基团的化合物为小分子，即不是聚合物、低聚物、树枝状聚合物或共聚物的分子。In one embodiment, the above-mentioned compound containing a crosslinking group is a small molecule, that is, a molecule which is not a polymer, an oligomer, a dendrimer or a copolymer.
在其中一个实施例中，上述含有交联基团的化合物具有空穴传输功能，使得该化合物能够应用于有机电子器件中。进一步地，上述含有交联基团的化合物能够作为OLED中的空穴传输层的材料。In one embodiment, the above-mentioned compound containing a crosslinking group has a hole transporting function, so that the compound can be applied to an organic electronic device. Further, the above-mentioned compound containing a crosslinking group can be used as a material of a hole transport layer in an OLED.
在其中一个实施例中，上述含有交联基团的化合物具有较高的LUMO(Lowest Un℃cupied Molecular Orbital，最低未占分子轨道)能级，使得该化合物具有电子阻挡功能，能够用于有机电子器件中。进一步地，上述含有交联基团的化合物能够作为OLED中的电子阻挡层的材料。需要说明的是，本实施例中的较高的LUMO能级是指含有该化合物的功能层的LUMO能级高于相邻的功能层的LUMO能级，例如在OLED中，当该化合物作为电子阻挡层的材料时，电子阻挡层的LUMO能级高于发光层的LUMO能级。In one embodiment, the above-mentioned compound containing a crosslinking group has a high LUMO (Lowest Un°Ccupied Molecular Orbital) level, so that the compound has an electron blocking function and can be used for organic electrons. In the device. Further, the above-mentioned compound containing a crosslinking group can be used as a material of an electron blocking layer in an OLED. It should be noted that the higher LUMO energy level in the present embodiment means that the LUMO energy level of the functional layer containing the compound is higher than the LUMO energy level of the adjacent functional layer, for example, in the OLED, when the compound is used as an electron. When the material of the barrier layer is used, the LUMO energy level of the electron blocking layer is higher than the LUMO energy level of the light emitting layer.
在其中一个实施例中，上述含有交联基团的化合物具有较高的三线态能级(T1)，使得该化合物具有三线态激子阻挡功能，能够用于有机电子器件中。进一步地，上述含有交联基团的化合物能够作为OLED中的激子阻挡层的材料。需要说明的是，本实施例中的较高的T1是指含有该化合物的功能层的T1高于相邻的功能层的T1，例如在磷光OLED中，当该化合物作为激子阻挡层的材料时，激子阻挡层的T1高于发光层的T1。In one embodiment, the above-mentioned compound containing a crosslinking group has a higher triplet level (T 1 ), so that the compound has a triplet exciton blocking function and can be used in an organic electronic device. Further, the above-mentioned compound containing a crosslinking group can be used as a material of an exciton blocking layer in an OLED. Incidentally, in the embodiment of a high T 1 of the present embodiment refers to a functional layer of the compound is higher than T 1 T adjacent functional layer 1, the phosphorescent OLED for example, when the compound as an exciton blocking the material layer, the exciton blocking layer is higher than the T 1 T 1 of the light emitting layer.
在其中一个实施例中，上述含有交联基团的化合物具有较高的单线态能级S1，使得该化合物具有单线态激子阻挡功能，能够用于有机电子器件中。进一步地，上述含有交联基团的化合物能够作为OLED中的激子阻挡层的材料。需要说明的是，本实施例中的较高的S1是指含有该化合物的功能层的S1高于相邻的功能层的S1，例如在荧光OLED中，当该化合物作为激子阻挡层的材料时，激子阻挡层的S1高于发光层的S1。In one embodiment, the above-described compound containing a crosslinking group has a higher singlet energy level S 1 , so that the compound has a singlet exciton blocking function and can be used in an organic electronic device. Further, the above-mentioned compound containing a crosslinking group can be used as a material of an exciton blocking layer in an OLED. Incidentally, in the embodiment according to the present embodiment higher S S 1 refers to the compound containing the functional layer 1 is higher than the adjacent functional layers S 1, for example, a fluorescent OLED when the exciton blocking compound the material layer, the exciton blocking layer is greater than S 1 S 1 of the light emitting layer.
在其中一个实施例中，结构式(I)省去CLG后，得到结构式(I-1)：In one of the embodiments, after the structural formula (I) omits the CLG, the structural formula (I-1) is obtained:
Figure PCTCN2017118065-appb-000026
Figure PCTCN2017118065-appb-000026
在其中一个实施例中，结构式(I-1)的化合物具有较高的LUMO。进一步地，结构式(I-1)的化合物大于或等-2.7eV。进一步地，结构式(I-1)的化合物大于或等-2.6eV。进一步地，结构式(I-1)的化合物大于或等-2.5eV。进一步地，结构式(I-1)的化合物大于或等-2.4eV。In one embodiment, the compound of formula (I-1) has a higher LUMO. Further, the compound of the formula (I-1) is greater than or equal to -2.7 eV. Further, the compound of the formula (I-1) is greater than or equal to -2.6 eV. Further, the compound of the formula (I-1) is greater than or equal to -2.5 eV. Further, the compound of the formula (I-1) is greater than or equal to -2.4 eV.
在其中一个实施例中，结构式(I-1)的化合物的HOMO小于或等于-5.0eV，其中，HOMO表示最高已占轨道。进一步地，结构式(I-1)的化合物的HOMO小于或等于-5.1eV。进一步地，结构式(I-1)的化合物的HOMO小于或等于-5.2eV。 In one embodiment, the HOMO of the compound of formula (I-1) is less than or equal to -5.0 eV, wherein HOMO represents the highest occupied orbital. Further, the compound of the formula (I-1) has a HOMO of less than or equal to -5.1 eV. Further, the compound of the formula (I-1) has a HOMO of less than or equal to -5.2 eV.
在其中一个实施例中，结构式(I-1)的化合物的(HOMO-1)-HOMO大于或等于0.3eV，其中，(HOMO-1)表示第二高的已占轨道。进一步地，结构式(I-1)的化合物的(HOMO-1)-HOMO大于或等于0.35eV。进一步地，结构式(I-1)的化合物的(HOMO-1)-HOMO大于或等于0.4eV。进一步地，结构式(I-1)的化合物的(HOMO-1)-HOMO大于或等于0.45eV。In one embodiment, (HOMO-1)-HOMO of the compound of formula (I-1) is greater than or equal to 0.3 eV, wherein (HOMO-1) represents the second highest occupied orbital. Further, the compound of the formula (I-1) has a (HOMO-1)-HOMO of greater than or equal to 0.35 eV. Further, the compound of the formula (I-1) has a (HOMO-1)-HOMO of greater than or equal to 0.4 eV. Further, the (HOMO-1)-HOMO of the compound of the formula (I-1) is greater than or equal to 0.45 eV.
在其中一个实施例中，结构式(I-1)的化合物的三线态能级(T1)大于或等于2.5eV。进一步地，结构式(I-1)的化合物的T1大于或等于2.6eV。进一步地，结构式(I-1)的化合物的T1大于或等于2.7eV。In one embodiment, the compound of formula (I-1) has a triplet energy level (T 1 ) greater than or equal to 2.5 eV. Further, the compound of the formula (I-1) has a T 1 greater than or equal to 2.6 eV. Further, the compound of the formula (I-1) has a T 1 greater than or equal to 2.7 eV.
在其中一个实施方式中，HOMO能级和LUMO能级均可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)，也均可以通过CV(循环伏安法)进行测定，还均可以通过量子化学方法进行测定，例如DFT(密度泛函理论)。In one embodiment, both the HOMO level and the LUMO level can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy), and both can pass CV (cyclic voltammetry) The measurement can also be carried out by quantum chemical methods such as DFT (density functional theory).
在其中一个实施方式中，三线态能级T1可通过低温时间分辨发光光谱来测量，也可以通过量子模拟计算得到，例如通过Time-dependent DFT模拟计算或通过商业软件Gaussian 03W(Gaussian Inc.)模拟计算。其中，具体的模拟模拟方法可参见WO2011141110。In one embodiment, the triplet energy level T1 can be measured by low temperature time resolved luminescence spectroscopy or by quantum simulation, for example by Time-dependent DFT simulation or by commercial software Gaussian 03W (Gaussian Inc.). Calculation. Among them, the specific simulation method can be found in WO2011141110.
当然，需要说明的是，HOMO、LUMO及T1的绝对值取决于所用的测量方法、计算方法或评价方法。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。不同方法确定的能级值应进行相互标定。在本实施方式中，HOMO、LUMO及T1的值是基于Time-dependent DFT的模拟，但不影响其他测量方法或计算方法的应用。Of course, it should be noted that the absolute values of HOMO, LUMO, and T1 depend on the measurement method, calculation method, or evaluation method used. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. The energy level values determined by different methods should be calibrated against each other. In the present embodiment, the values of HOMO, LUMO, and T1 are simulations based on Time-dependent DFT, but do not affect the application of other measurement methods or calculation methods.
在其中一个实施例中，含有交联基团的化合物中，SP3杂化的基团的总量小于或等于总分子量的30％。较少的SP3杂化基团的存在能够有效保证上述含有交联基团的化合物的热稳定性，进而保证包括该化合物的器件的稳定性。进一步地，含有交联基团的化合物中，SP3杂化的基团的总量小于或等于总分子量的20％。进一步地，含有交联基团的化合物中，SP3杂化的基团的总量小于或等于总分子量的10％。In one embodiment, the total amount of SP 3 hybridized groups in the compound containing a crosslinking group is less than or equal to 30% of the total molecular weight. The presence of fewer SP 3 hybrid groups is effective to ensure the thermal stability of the above-described crosslinking group-containing compound, thereby ensuring the stability of the device including the compound. Further, in the compound containing a crosslinking group, the total amount of the SP 3 hybridized group is less than or equal to 20% of the total molecular weight. Further, in the compound containing a crosslinking group, the total amount of the SP 3 hybridized group is less than or equal to 10% of the total molecular weight.
在其中一个实施例中，含有交联基团的化合物的玻璃化转化温度小于或等于100℃。进一步地，含有交联基团的化合物的玻璃化转化温度小于或等于120℃。进一步地，含有交联基团的化合物的玻璃化转化温度小于或等于140℃。进一步地，含有交联基团的化合物的玻璃化转化温度小于或等于160℃。进一步地，含有交联基团的化合物的玻璃化转化温度小于或等于180℃。In one embodiment, the crosslinking group-containing compound has a glass transition temperature of less than or equal to 100 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 120 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 140 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 160 °C. Further, the compound having a crosslinking group has a glass transition temperature of less than or equal to 180 °C.
在其中一个实施例中，含有交联基团的化合物的摩尔质量大于或等于700g/mol，使得该化合物能够作为印刷型OLED的原料。进一步地，摩尔质量大于或等于800g/mol。进一步地，含有交联基团的化合物的摩尔质量大于或等于900g/mol。进一步地，含有交联基团的化合物的摩尔质量大于或等于1000g/mol。进一步地，含有交联基团的化合物的摩尔质量大于或等于1100g/mol。In one embodiment, the compound having a crosslinking group has a molar mass of greater than or equal to 700 g/mol, so that the compound can be used as a raw material for a printed OLED. Further, the molar mass is greater than or equal to 800 g/mol. Further, the compound having a crosslinking group has a molar mass of greater than or equal to 900 g/mol. Further, the compound having a crosslinking group has a molar mass of greater than or equal to 1000 g/mol. Further, the compound having a crosslinking group has a molar mass of greater than or equal to 1100 g/mol.
在其中一个实施例中，含有交联基团的化合物于25℃下在甲苯中的溶解度大于或等于10mg/mL。进一步地，含有交联基团的化合物于25℃下在甲苯中的溶解度大于或等于15mg/mL。含有交联基团的化合物于25℃下在甲苯中的溶解度大于或等于20mg/mL。In one embodiment, the compound containing a crosslinking group has a solubility in toluene of greater than or equal to 10 mg/mL at 25 °C. Further, the compound having a crosslinking group has a solubility in toluene at 25 ° C of 15 mg/mL or more. The compound containing a crosslinking group has a solubility in toluene of greater than or equal to 20 mg/mL at 25 °C.
在其中一个实施例中，含有交联基团的化合物的结构式选自如下结构式中的一种：In one embodiment, the structural formula of the compound containing a crosslinking group is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000027
Figure PCTCN2017118065-appb-000027
Figure PCTCN2017118065-appb-000028
Figure PCTCN2017118065-appb-000028
Figure PCTCN2017118065-appb-000029
Figure PCTCN2017118065-appb-000029
Figure PCTCN2017118065-appb-000030
Figure PCTCN2017118065-appb-000030
Figure PCTCN2017118065-appb-000031
Figure PCTCN2017118065-appb-000032
上述结构式中，一个结构式代表一种物质，相邻结构式之间的交错仅是文档排版问题，不具有其他意义。
Figure PCTCN2017118065-appb-000031
Figure PCTCN2017118065-appb-000032
In the above structural formula, one structural formula represents a substance, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other meaning.
上述含有交联基团的化合物至少具有如下优点：The above compound containing a crosslinking group has at least the following advantages:
(1)上述含有交联基团的化合物包含有机功能结构单元和可交联基团，具有好的溶解性和成膜性。该化合物可以通过加热处理或紫外照射，使分子间的可交联基团发生交联反应，从而使该化合物固化形成薄膜。同时，由于上述化合物具有较好的溶解性和成膜性，使得含有该化合物的组合物具有较好的印刷性及成膜性能，进而使得含有该化合物或该组合物的电子器件具有较长的寿命及较高的性能，最终使得电子器件的制造成本低、效率高；(1) The above-mentioned compound containing a crosslinking group contains an organic functional structural unit and a crosslinkable group, and has good solubility and film formability. The compound can be crosslinked by heat treatment or ultraviolet irradiation to crosslink the intermolecular crosslinkable groups, thereby curing the compound to form a film. At the same time, since the above compound has good solubility and film-forming property, the composition containing the compound has good printability and film-forming property, thereby making the electronic device containing the compound or the composition longer. The longevity and high performance ultimately result in low manufacturing cost and high efficiency of the electronic device;
(2)上述含有交联基团的化合物具有空穴传输功能，使得该化合物能够应用于有机电子器件中；(2) The above-mentioned compound containing a crosslinking group has a hole transporting function, so that the compound can be applied to an organic electronic device;
(3)上述含有交联基团的化合物具有较高的LUMO能级，使得该化合物具有电子阻挡功能，能够用于有机电子器件中；(3) The above-mentioned compound containing a crosslinking group has a high LUMO energy level, so that the compound has an electron blocking function and can be used in an organic electronic device;
(4)上述含有交联基团的化合物具有较高的三线态能级，使得该化合物具有三线态激子阻挡功能，能够用于有机电子器件中；(4) The above compound having a crosslinking group has a higher triplet energy level, so that the compound has a triplet exciton blocking function and can be used in an organic electronic device;
(5)上述含有交联基团的化合物具有较高的单线态能级，使得该化合物具有单线态激子阻挡功能，能够用于有机电子器件中； (5) The above compound having a crosslinking group has a higher singlet energy level, so that the compound has a singlet exciton blocking function and can be used in an organic electronic device;
(6)上述含有交联基团的化合物中，SP3杂化的基团的总量小于或等于总分子量的30％，较少的SP3杂化基团的存在能够有效保证上述含有交联基团的化合物的热稳定性，进而保证包括该化合物的器件的稳定性。(6) In the above compound containing a crosslinking group, the total amount of the SP 3 hybridized group is less than or equal to 30% of the total molecular weight, and the presence of a small amount of the SP 3 hybrid group can effectively ensure the above-mentioned crosslinking. The thermal stability of the compound of the group, thereby ensuring the stability of the device comprising the compound.
上述含有交联基团制备时，使用含有活性基团的原料进行反应即可。When the above-mentioned crosslinking group-containing group is prepared, the reaction may be carried out using a raw material containing a reactive group.
在其中一个实施例中，含有活性基团的原料包含上述含有交联基团的化合物结构式(I)中的结构单元A和结构单元SG和至少一种离去基团。In one embodiment, the active group-containing raw material comprises the structural unit A and the structural unit SG and at least one leaving group in the structural formula (I) of the above-mentioned compound having a crosslinking group.
在其中一个实施例中，离去基团为溴，碘，硼酸或硼酸酯。In one embodiment, the leaving group is bromine, iodine, boric acid or a boronic ester.
需要说明的是，形成C-C连接的反应为本领域技术人员熟知的反应，此处不再赘述。进一步地，形成C-C连接的反应为偶联反应。更进一步地，形成C-C连接的反应为SUZUKI偶联反应(铃木反应)、STILLE偶联反应(施蒂勒反应)或HECK偶联反应(赫克反应)。It should be noted that the reaction for forming a C-C linkage is a reaction well known to those skilled in the art and will not be described herein. Further, the reaction that forms a C-C linkage is a coupling reaction. Further, the reaction for forming a C-C linkage is a SUZUKI coupling reaction (Suzuki reaction), a STILLE coupling reaction (Stiler reaction) or a HECK coupling reaction (Heck reaction).
一实施方式的混合物，包括上述实施方式的含有交联基团的化合物及有机功能材料。The mixture of one embodiment includes the crosslinking group-containing compound and the organic functional material of the above embodiment.
在其中一个实施例中，有机功能材料选自空穴注入材料(HIM)、空穴传输材料(HTM)、空穴阻挡材料(HBM)、电子注入材料(EIM)、电子传输材料(ETM)、电子阻挡材料(EBM)、有机基质材料(Host)、单重态发光体(荧光发光体)、三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料中的至少一种。。In one embodiment, the organic functional material is selected from the group consisting of hole injection materials (HIM), hole transport materials (HTM), hole blocking materials (HBM), electron injecting materials (EIM), electron transport materials (ETM), At least one of an electron blocking material (EBM), an organic matrix material (Host), a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant), a thermally excited delayed fluorescent material (TADF material), and an organic dye One. .
在其中一个实施例中，混合物包括上述含有交联基团的化合物和荧光发光体。需要说明的是，上述含有交联基团的化合物可以作为主体材料或与其他材料共同作为主体材料。In one embodiment, the mixture comprises the above-described compound containing a crosslinking group and a fluorescent illuminant. It should be noted that the above-mentioned compound containing a crosslinking group may be used as a host material or as a host material together with other materials.
在其中一个实施例中，混合物包括上述含有交联基团的化合物和TADF材料。In one embodiment, the mixture comprises the above-described compound containing a crosslinking group and a TADF material.
下面对单重态发光体、三重态发光体和TADF材料作一些较详细的描述(但不限于此)。The following describes some of the singlet emitters, triplet emitters, and TADF materials in some detail (but is not limited thereto).
单重态发光体(Singlet Emitter)Singlet emitter (Singlet Emitter)
单重态发光体往往有较长的共轭π电子***。迄今，已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物、在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物。Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
在其中一个实施例中，单重态发光体为一元苯乙烯胺、二元苯乙烯胺、三元苯乙烯胺、四元苯乙烯胺、苯乙烯膦、苯乙烯醚或芳胺。In one embodiment, the singlet illuminant is a monostyrylamine, a dibasic styrylamine, a ternary styrylamine, a quaternary styrylamine, a styrene phosphine, a styrene ether or an aromatic amine.
一元苯乙烯胺为包含一个无取代或取代的苯乙烯基和至少一个胺的化合物。进一步地，一元苯乙烯胺中的胺为芳香胺。二元苯乙烯胺为包含二个无取代或取代的苯乙烯基和至少一个胺的化合物。进一步地，二元苯乙烯胺中的胺为芳香胺。三元苯乙烯胺为包含三个无取代或取代的苯乙烯基和至少一个胺的化合物。进一步地，三元苯乙烯胺中的胺为芳香胺。四元苯乙烯胺为包含四个无取代或取代的苯乙烯基和至少一个胺的化合物。进一步地，四元苯乙烯胺中的胺为芳香胺。苯乙烯膦为包含苯乙烯基和至少一个膦的化合物。苯乙烯醚包含苯乙烯基和至少一个醚的化合物。The monostyrylamine is a compound containing an unsubstituted or substituted styryl group and at least one amine. Further, the amine in the monobasic styrene amine is an aromatic amine. The binary styrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine. Further, the amine in the dibasic styrylamine is an aromatic amine. The ternary styrylamine is a compound containing three unsubstituted or substituted styryl groups and at least one amine. Further, the amine in the ternary styrylamine is an aromatic amine. The quaternary styrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine. Further, the amine in the tetrabasinamine is an aromatic amine. Styrene phosphine is a compound comprising a styryl group and at least one phosphine. The styrene ether comprises a compound of a styryl group and at least one ether.
在其中一个实施例中，苯乙烯基为二苯乙烯基。需要说明的是，取代的二苯乙烯基也可以作为本实施例的苯乙烯基。In one embodiment, the styryl group is a distyryl group. It should be noted that a substituted distyryl group can also be used as the styryl group of the present embodiment.
芳香胺为包含三个直接联接氮的无取代或取代的芳基或三个直接联接氮的无取代或取代的杂芳基的化合物。进一步地，芳香胺中的芳基或杂芳基中至少含有一个稠环，且芳基或杂芳基中的环原子数至少为14。进一步地，芳香胺为芳香蒽胺、芳香蒽二胺、芳香芘胺、芳香芘二胺、芳香屈胺或芳香屈二胺。芳香蒽胺为一个二元芳香胺基直接与蒽连接的化合物。具体地，芳香蒽胺为一个二元芳香胺基直接与蒽的9号碳原子连接的化合物。芳香蒽二胺为二个二元芳基胺基团直接与蒽连接的化合物。具体地，芳香蒽胺为二个二元芳香胺基分别与蒽的9号和10号碳原子连接的化合物。芳香芘胺为一个二元芳香胺基直接与芘连接的化合物。具体地，芳香芘胺为一个二元芳香胺基直接与芘的1号碳原子连接的化合物。芳香芘二胺为两个二元芳香胺基直接与芘连接的化合物。具体地，芳香二胺为两个二元芳香胺基分别与芘的1号和6号碳原子连接的化合物。芳香屈胺为一个二元芳香胺基直接与屈连接的化合物。具体地，芳香芘胺为一个二元芳香胺基直接与屈的1号碳原子连接的化合物。芳香屈二胺为两个二元芳香胺基直接与屈连接的化合物。具体地，芳香屈二胺为两个二元芳香胺基分别与屈的1号和6号碳原子连接的化合物。The aromatic amine is a compound containing three unsubstituted or substituted aryl groups directly bonded to nitrogen or three unsubstituted or substituted heteroaryl groups directly bonded to nitrogen. Further, the aryl or heteroaryl group in the aromatic amine contains at least one fused ring, and the number of ring atoms in the aryl or heteroaryl group is at least 14. Further, the aromatic amine is an aromatic guanamine, an aromatic guanidine diamine, an aromatic guanamine, an aromatic guanidine diamine, an aromatic thiamine or an aromatic quinone diamine. Aromatic decylamine is a compound in which a binary aromatic amine group is directly bonded to hydrazine. Specifically, the aromatic decylamine is a compound in which a binary aromatic amine group is directly bonded to the carbon atom No. 9 of hydrazine. An aromatic quinone diamine is a compound in which two diaryl arylamine groups are directly attached to hydrazine. Specifically, the aromatic guanamine is a compound in which two binary aromatic amine groups are bonded to the carbon atoms of No. 9 and No. 10, respectively. Aromatic decylamine is a compound in which a binary aromatic amine group is directly bonded to hydrazine. Specifically, the aromatic decylamine is a compound in which a divalent aromatic amine group is directly bonded to the carbon atom No. 1 of hydrazine. An aromatic quinone diamine is a compound in which two binary aromatic amine groups are directly bonded to hydrazine. Specifically, the aromatic diamine is a compound in which two binary aromatic amine groups are bonded to the carbon atoms of No. 1 and No. 6 of ruthenium, respectively. Aromatic thiamine is a compound in which a binary aromatic amine group is directly attached to a bend. Specifically, the aromatic guanamine is a compound in which a divalent aromatic amine group is directly bonded to the carbon atom No. 1 of the bend. An aromatic quinone diamine is a compound in which two binary aromatic amine groups are directly bonded to a bend. Specifically, the aromatic quinone diamine is a compound in which two binary aromatic amine groups are bonded to the carbon atoms of No. 1 and No. 6 respectively.
具体地，基于乙烯胺的单重态发光体或基于芳胺的单重态发光体例如可以是WO  2006/000388、WO 2006/058737、WO 2006/000389、WO 2007/065549、WO 2007/115610、US 7250532 B2、DE 102005058557 A1、CN 1583691 A、JP 08053397 A、US 6251531 B1、US 2006/210830 A、EP 1957606 A1和US 2008/0113101 A1中的单重态发光体。上述专利文件中的单重态发光体均可以作为本实施方式的单重态发光体。In particular, the monoamine illuminant based on vinylamine or the singlet illuminant based on arylamine may for example be WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, Singlet emitters in EP 1957606 A1 and US 2008/0113101 A1. The singlet illuminants in the above patent documents can be used as the singlet illuminators of the present embodiment.
基于均二苯乙烯极其衍生物的单重态发光体例如可以是US 5121029A中的单重态发光体。The singlet illuminant based on the stilbene extreme derivative may, for example, be a singlet illuminant in US Pat. No. 5,121,029 A.
在其中一个实施例中，单重态发光体为茚并芴-胺或茚并芴-二胺，如WO 2006/122630所公开的单重态发光体。进一步地，单重态发光体为苯并茚并芴-胺或苯并茚并芴-二胺，如WO 2008/006449所公开的单重态发光体。进一步地，单重态发光体为二苯并茚并芴-胺或二苯并茚并芴-二胺，如WO2007/140847所公开的单重态发光体。In one embodiment, the singlet emitter is an indeno-amine or an indeno-diamine, such as the singlet emitter disclosed in WO 2006/122630. Further, the singlet emitter is a benzoindolo-amine or a benzoindolo-diamine, such as the singlet emitter disclosed in WO 2008/006449. Further, the singlet emitter is dibenzoindolo-amine or dibenzoindolo-diamine, such as the singlet emitter disclosed in WO2007/140847.
需要说明的是，多环芳烃化合物及其衍生物可以作为单重态发光体的材料。例如可以是蒽[如9,10-二(2-萘并蒽)]、萘、四苯、氧杂蒽、菲、芘(如2,5,8,11-四-t-丁基苝)、茚并芘、苯撑(如4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)、二茚并芘、十环烯、六苯并苯、芴、螺二芴、芳基芘(如US20060222886A)、亚芳香基乙烯(如US5121029A，US5130603A)、环戊二烯(四苯基环戊二烯)、红荧烯、香豆素、若丹明、喹吖啶酮、吡喃(如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃，DCM)、噻喃、双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1)、双(吖嗪基)亚甲基化合物、carbostyryl化合物、噁嗪酮、苯并恶唑、苯并噻唑、苯并咪唑、吡咯并吡咯二酮及上述化合物的衍生物。一些单重态发光体的材料可在下述专利文件中找到：US 20070252517 A1、US 4769292 A、US 6020078 A、US 2007/0252517 A1及US 2007/0252517 A1。特此将上述列出的专利文件中的单重态发光体的材料并入本实施方式中作为参考。It should be noted that the polycyclic aromatic hydrocarbon compound and its derivative can be used as a material of a singlet illuminant. For example, it may be 蒽 [such as 9,10-di(2-naphthoquinone)], naphthalene, tetraphenyl, xanthene, phenanthrene, anthracene (such as 2,5,8,11-tetra-t-butylhydrazine) , anthracene, phenylene (such as 4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1'-biphenyl), indenylindole, decacycloolefin, hexabenzo Benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886A), arylene vinyl (such as US5121029A, US5130603A), cyclopentadiene (tetraphenylcyclopentadiene), rubrene, coumarin, Danming, quinacridone, pyran (such as 4 (dicyanomethylidene)-6-(4-p-dimethylaminostyryl-2-methyl)-4H-pyran, DCM), thiophene Borane, bis(pyridazinyl)imide boron compound (US 2007/0092753 A1), bis(pyridazinyl)methylene compound, carbostyryl compound, oxazinone, benzoxazole, benzothiazole, benzimidazole , pyrrolopyrroledione and derivatives of the above compounds. Materials for some singlet illuminants can be found in the following patent documents: US 20070252517 A1, US 4769292 A, US 6020078 A, US 2007/0252517 A1 and US 2007/0252517 A1. The materials of the singlet emitters in the above-listed patent documents are hereby incorporated by reference in their entireties.
在其中一个实施例中，单重态发光体选自如下结构式中的一种：In one embodiment, the singlet emitter is selected from one of the following structural formulae:
Figure PCTCN2017118065-appb-000033
Figure PCTCN2017118065-appb-000033
三重态发光体(磷光发光体)Triplet emitter (phosphorescent emitter)
三重态发光体也称磷光发光体。Triplet emitters are also known as phosphorescent emitters.
在其中一个实施例中，三重态发光体为金属络合物，且结构式为M(L)n；其中，M为金属原子，L为有机配体，且L通过一个或多个位置与G以化学键或配位键的方式连接；n为大于1的整数。进一步地，n为1、2、3、4、5或6。需要说明的是，金属络合物通过一个或多个位置联接到聚合物得到的化合物也可以作为三重态发光体。具体地，聚合物为有机配体。In one embodiment, the triplet emitter is a metal complex and has the formula M(L)n; wherein M is a metal atom, L is an organic ligand, and L is in one or more positions with G A chemical bond or a coordinate bond is attached; n is an integer greater than one. Further, n is 1, 2, 3, 4, 5 or 6. It should be noted that the compound obtained by coupling a metal complex to a polymer through one or more positions may also function as a triplet emitter. In particular, the polymer is an organic ligand.
在其中一个实施例中，M为过渡金属元素、镧系元素或锕系元素。进一步地，M为Ir、Pt、Pd、Au、Rh、Ru、Os、Sm、Eu、Gd、Tb、Dy、Re、Cu或Ag。更进一步地，M为Os、Ir、Ru、Rh、Re、Pd或Pt。In one embodiment, M is a transition metal element, a lanthanide or a lanthanide. Further, M is Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag. Further, M is Os, Ir, Ru, Rh, Re, Pd or Pt.
在其中一个实施例中，三重态发光体包含有螯合配体。螯合配体有利于提高金属络合物的稳定性。具体地，螯合配体通过至少两个结合点与金属原子配位。进一步地，三重态发光体包含有2～3个相同或不同的双齿或多齿配体。 In one embodiment, the triplet emitter comprises a chelating ligand. Chelating ligands are beneficial for increasing the stability of metal complexes. Specifically, the chelating ligand is coordinated to the metal atom through at least two bonding sites. Further, the triplet emitter comprises 2 to 3 identical or different bidentate or multidentate ligands.
在其中一个实施例中，有机配体为苯基吡啶衍生物、7,8-苯并喹啉衍生物、2(2-噻吩基)吡啶衍生物、2(1-萘基)吡啶衍生物或2苯基喹啉衍生物。上述有机配体均被取代基取代。取代基例如为含氟甲基或三氟甲基。在其中一个实施例中，三重态发光体为金属络合物时，还包括辅助配体。具体地，辅助配体为乙酸丙酮或苦味酸。In one embodiment, the organic ligand is a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative or 2 phenylquinoline derivatives. The above organic ligands are all substituted by a substituent. The substituent is, for example, a fluorine-containing methyl group or a trifluoromethyl group. In one embodiment, when the triplet emitter is a metal complex, an auxiliary ligand is also included. Specifically, the ancillary ligand is acetic acid acetone or picric acid.
在其中一个实施例中，可用作三重态发光体的金属络合物有如下结构式：In one embodiment, the metal complex that can be used as the triplet emitter has the following structural formula:
Figure PCTCN2017118065-appb-000034
Figure PCTCN2017118065-appb-000034
其中，G为金属原子；Ar1'为至少包含一个施主原子(即有一孤对电子的原子)的环状基团，且Ar1'通过施主原子与G连接；Ar1'至少包含有一个C原子的环状基团，且Ar2'通过C原子与G连接；Ar1'和Ar2'通过共价键连接；L'为辅助配体；m'为1、2或3；n'为0、1或2。Wherein G is a metal atom; Ar 1 ' is a cyclic group containing at least one donor atom (ie, an atom having a lone pair of electrons), and Ar 1 ' is bonded to G through a donor atom; Ar 1 ' contains at least one C a cyclic group of an atom, and Ar 2 ' is bonded to G through a C atom; Ar 1 ' and Ar 2 ' are linked by a covalent bond; L' is an ancillary ligand; m' is 1, 2 or 3; n' is 0, 1 or 2.
具体地，Ar1'和Ar2'均可以携带一个或多个取代基团。其中，取代基团为氧、苯基或二苯并呋喃，Ar1'和Ar2'能够通过两者的取代基团连接。进一步地，三重态发光体的一个结构式中，m'个Ar1'可以为相同的基团，也可以为不同的基团；m'个Ar2'可以为相同的基团，也可以为不同的基团；n'个L'可以为相同的基团，也可以为不同的基团。Specifically, both Ar 1 'and Ar 2 ' may carry one or more substituent groups. Wherein the substituent group is oxygen, phenyl or dibenzofuran, and Ar 1 ' and Ar 2 ' can be linked by a substituent group of both. Further, in one structural formula of the triplet emitter, m'Ar 1 ' may be the same group or different groups; m'Ar 2 ' may be the same group or different a group; n'L' may be the same group or a different group.
进一步地，Ar1'为至少包含一个施主原子的环状基团时，施主原子为氮或磷。Further, when Ar 1 'is a cyclic group containing at least one donor atom, the donor atom is nitrogen or phosphorus.
进一步地，m'为2或3。更进一步地，m'为3。Further, m' is 2 or 3. Further, m' is 3.
进一步地，n'为0或1。更进一步地，n'为0。Further, n' is 0 or 1. Further, n' is 0.
在其中一个实施例中，一些三重态发光体的材料及其应用的例子可在下述专利文件和文献中找到:WO 200070655、WO 200141512、WO 200202714、WO 200215645、EP 1191613、EP 1191612、EP 1191614、WO 2005033244、WO 2005019373、US 2005/0258742、WO 2009146770、WO 2010015307、WO 2010031485、WO 2010054731、WO 2010054728、WO 2010086089、WO 2010099852、WO 2010102709、US 20070087219 A1、US 20090061681 A1、US 20010053462 A1、Baldo,Thompson et al.Nature 403,(2000),750-753、US 20090061681 A1、US 20090061681 A1、Adachi et al.Appl.Phys.Lett.78(2001),1622-1624、J.Kido et al.Appl.Phys.Lett.65(1994),2124、Kido et al.Chem.Lett.657,1990、US 2007/0252517 A1、Johnson et al.,JACS 105,1983,1795、Wrighton,JACS 96,1974,998、Ma et al.,Synth.Metals 94,1998,245、US 6824895、US 7029766、US 6835469、US 6830828、US 20010053462 A1、WO 2007095118A1、US 2012004407A1、WO 2012007088A1、WO2012007087A1、WO 2012007086A1、US 2008027220A1、WO 2011157339A1、CN 102282150A、WO 2009118087A1。特此将上述列出的专利文件和文献中的三重态发光体的材料并入本实施方式中。In one of the embodiments, examples of materials for some triplet emitters and their use can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson Et al. Nature 403, (2000), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys .Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma. Et al., Synth.Metals 94, 1998, 245, US Pat. No. 6,824,895, US Pat. No. 7,029,766, US Pat. No. 6,835,469, US Pat. No. 6, 030, 828, US Pat. 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1. The materials listed above and the materials of the triplet emitters in the literature are hereby incorporated into the present embodiment.
在其中一个实施例中，三重态发光体可选自如下表中结构式中的一种：In one embodiment, the triplet emitter can be selected from one of the structural formulae in the following table:
Figure PCTCN2017118065-appb-000035
Figure PCTCN2017118065-appb-000035
Figure PCTCN2017118065-appb-000036
Figure PCTCN2017118065-appb-000036
Figure PCTCN2017118065-appb-000037
Figure PCTCN2017118065-appb-000037
热激发延迟荧光发光材料(TADF材料)Thermally Excited Delayed Fluorescent Luminescent Material (TADF Material)
传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔEst)，三线态激子可以通过反系间穿越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子。器件内量子效率可达到100％。同时材料结构可控，性质稳定，价格便宜无需要贵金属，在OLED领域的应用前景广阔。Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
TADF材料需要具有较小的单线态-三线态能级差(即ΔEst)。具体地，TADF材料的ΔEst小于0.3eV。进一步地，TADF材料的ΔEst小于0.2eV。进一步地，TADF材料的ΔEst小于0.1eV。TADF有较好的荧光量子效率。一些TADF材料可在下述专利文件中找到：CN103483332(A)、TW201309696(A)、TW201309778(A)、TW201343874(A)、TW201350558(A)、US20120217869(A1)、WO2013133359(A1)、WO2013154064(A1)、Adachi,et.al.Adv.Mater.,21,2009,4802、Adachi,et.al.Appl.Phys.Lett.,98,2011,083302、Adachi,et.al.Appl.Phys.Lett.,101,2012,093306、Adachi,et.al.Chem.Commun.,48,2012,11392、Adachi,et.al.Nature Photonics,6,2012,253、Adachi,et.al.Nature,492,2012,234、Adachi,et.al.J.Am.Chem.S℃,134,2012,14706、Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311、Adachi,et.al.Chem.Commun.,48,2012,9580、Adachi,et.al.Chem.Commun.,48,2013,10385、Adachi,et.al.Adv.Mater.,25,2013,3319、Adachi,et.al.Adv.Mater.,25,2013,3707、Adachi,et.al.Chem.Mater.,25,2013,3038、Adachi,et.al.Chem.Mater.,25,2013,3766、Adachi,et.al.J.Mater.Chem.C.,1,2013,4599、Adachi,et.al.J.Phys.Chem.A.,117,2013,5607。特此将上述列出的专利或文章文件中的全部TADF材料并入本实施方式中。The TADF material needs to have a small singlet-triplet energy level difference (ie, ΔEst). Specifically, the ΔEst of the TADF material is less than 0.3 eV. Further, the ΔEst of the TADF material is less than 0.2 eV. Further, the ΔEst of the TADF material is less than 0.1 eV. TADF has a good fluorescence quantum efficiency. Some TADF materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1) , Adachi, et.al.Adv.Mater., 21, 2009, 4802, Adachi, et.al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012, 234, Adachi, et. al. J. Am. Chem. S°C, 134, 2012, 14706, Adachi, et. al. Angew. Chem. Int. Ed, 51, 2012, 11311, Adachi, et. .Commun., 48, 2012, 9580, Adachi, et. al. Chem. Commun., 48, 2013, 10385, Adachi, et. al. Adv. Mater., 25, 2013, 3319, Adachi, et. Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et. J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607. All TADF materials in the above listed patents or article documents are hereby incorporated into this embodiment.
在其中一个实施例中，TADF材料可选自下表的结构式中的一种： In one embodiment, the TADF material can be selected from one of the structural formulae of the following table:
Figure PCTCN2017118065-appb-000038
Figure PCTCN2017118065-appb-000039
上述结构式中，一个结构式代表一种TADF材料，相邻结构式之间的交错仅是文档排版问题，不具有其他意义。以上出现的用于有机功能结构单元的有机功能材料出版物为公开的目的以参考方式并入本申请。
Figure PCTCN2017118065-appb-000038
Figure PCTCN2017118065-appb-000039
In the above structural formula, one structural formula represents a TADF material, and the interleaving between adjacent structural formulas is only a problem of document typesetting, and has no other meaning. The organic functional material publications for organic functional structural units appearing above are hereby incorporated by reference.
一实施方式的组合物，包括上述实施方式的含有交联基团的化合物及上述实施方式的混合物中的一种、有机溶剂。其中，有机溶剂选自芳族溶剂、芳杂族溶剂、酮类溶剂、醚类溶剂及酯类溶剂中的至少一种。进一步地，有机溶剂选自脂肪族链取代的芳族溶剂、脂肪族环取代的芳族溶剂、芳族酮溶剂及芳族醚溶剂中的至少一种。The composition of one embodiment includes one of the compound containing a crosslinking group of the above embodiment and the mixture of the above embodiment, and an organic solvent. The organic solvent is at least one selected from the group consisting of an aromatic solvent, an aromatic heteropoly solvent, a ketone solvent, an ether solvent, and an ester solvent. Further, the organic solvent is at least one selected from the group consisting of an aliphatic chain-substituted aromatic solvent, an aliphatic ring-substituted aromatic solvent, an aromatic ketone solvent, and an aromatic ether solvent.
具体地，芳族溶剂或芳杂族溶剂为对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、三戊苯、戊基甲苯、邻二甲苯、间二甲苯、对二甲苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、二己基苯、二丁基苯、对二异丙基苯、1-甲氧基萘、环己基苯、二甲基萘、3-异丙基联苯、对甲基异丙苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、N-甲基二苯胺、4-异丙基联苯、α,α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘或二苄醚。Specifically, the aromatic solvent or the aromatic hetero-solvent is p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-Methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2, 3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diiso Propylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene , 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1, 1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene or dibenzyl ether.
酮溶剂为1-四氢萘酮、2-四氢萘酮、2-(苯基环氧)四氢萘酮、6-(甲氧基)四氢萘酮、苯乙酮、苯丙酮、二苯甲酮及这些化合物的衍生物，衍生物例如可以是4-甲基苯乙酮、3-甲基苯乙酮、2-甲基苯乙酮、4-甲基苯丙酮、3-甲基苯丙酮、2-甲基苯丙酮，异佛尔酮、2,6,8-三甲基-4-壬酮、葑酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、佛尔酮或二正戊基酮。The ketone solvent is 1-tetralone, 2-tetralone, 2-(phenyl epoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, Benzophenone and derivatives of these compounds, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methyl Phenylacetone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2-nonanone, 3-fluorenone, 5-fluorenone, 2- Anthrone, 2,5-hexanedione, phorone or di-n-pentyl ketone.
醚溶剂为3-苯氧基甲苯、丁氧基苯、苄基丁基苯、对茴香醛二甲基乙缩醛、四氢-2-苯氧基-2H-吡喃、1,2-二甲氧基-4-(1-丙烯基)苯、1,4-苯并二噁烷、1,3-二丙基苯、2,5-二甲氧基甲苯、4-乙基本***、1,2,4-三甲氧基苯、4-(1-丙烯基)-1,2-二甲氧基苯、1,3-二甲氧基苯、缩水甘油基苯基醚、二苄基醚、4-叔丁基茴香醚、反式-对丙烯基茴香醚、1,2-二甲氧基苯、1-甲氧基萘、二苯醚、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、戊醚c己醚、二辛醚、乙二醇二丁醚、二乙二醇二***、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚或四乙二醇二甲醚。The ether solvent is 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-di Methoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenethyl ether, 1 , 2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether , 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-benzene Oxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether c hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl Ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
酯溶剂为辛酸烷酯、癸二酸烷酯、硬脂酸烷酯、苯甲酸烷酯、苯乙酸烷酯、肉桂酸烷酯、草酸烷酯、马来酸烷酯、烷内酯或油酸烷酯。The ester solvent is alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenyl acetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide or oleic acid. Alkyl ester.
酮溶剂为2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、2,6,8-三甲基-4-壬酮、佛尔酮或二正戊基酮。醚溶剂为戊醚、己醚、二辛醚、乙二醇二丁醚、二乙二醇二***、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚或四乙二醇二甲醚。The ketone solvent is 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, phorone or Di-n-pentyl ketone. The ether solvent is pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, Triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
在其中一个实施例中，上述组合物还包含有另一种有机溶剂。另一种有机溶剂选自甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷及茚中的至少一种。In one embodiment, the above composition further comprises another organic solvent. Another organic solvent is selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, and Xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin and hydrazine At least one.
在其中一个实施例中，上述组合物为溶液。In one embodiment, the above composition is a solution.
在其中一个实施例中，上述组合物为悬浮液。In one embodiment, the above composition is a suspension.
需要说明的是，上述组合物为溶液或悬浮液时，上述组合物还可以包含其他组分中的一种。其他组分用于调节溶液或悬浮液的粘度、成膜性能或提高附着性等。其他组分例如可以是表面活性化合物、润滑剂、润湿剂、分散剂、疏水剂或粘接剂。有关打印技术及其对有关溶液的相关要求(如溶剂、浓度及粘度等)的详细信息请参见Helmut Kipphan主编的《印刷 媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。It should be noted that when the above composition is a solution or a suspension, the above composition may further comprise one of the other components. Other components are used to adjust the viscosity of the solution or suspension, film forming properties or to improve adhesion and the like. The other components may, for example, be surface-active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents or binders. For more information on printing techniques and their requirements for solutions (such as solvents, concentrations and viscosities), see Helmut Kipphan's "Printing" Handbook of Print Media: Technologies and Production Methods, ISBN 3-540-67326-1.
上述组合物能够作为油墨，用于印刷。用于印刷工艺时，油墨的粘度、表面张力均为重要的参数。合适的的表面张力使得油墨能够适合于特定的基板和特定的印刷方法。The above composition can be used as an ink for printing. When used in the printing process, the viscosity and surface tension of the ink are important parameters. A suitable surface tension allows the ink to be adapted to a particular substrate and to a particular printing method.
在其中一个实施例中，油墨在工作温度或在25℃下的表面张力为19dyne/cm～50dyne/cm。进一步地，油墨在工作温度或在25℃下的表面张力为22dyne/cm～35dyne/cm。进一步地，油墨在工作温度或在25℃下的表面张力为25dyne/cm～33dyne/cm。In one of the embodiments, the ink has a surface tension of from 19 dyne/cm to 50 dyne/cm at an operating temperature or at 25 °C. Further, the ink has a surface tension of 22 dyne/cm to 35 dyne/cm at an operating temperature or at 25 °C. Further, the ink has a surface tension of 25 dyne/cm to 33 dyne/cm at an operating temperature or at 25 °C.
在其中一个实施例中，油墨在工作温度或25℃下的粘度为1cps～100cps，较低的粘度使得油墨能够适用于喷墨印刷。进一步地，油墨在工作温度或25℃下的粘度为1cps～50cps。进一步地，油墨在工作温度或25℃下的粘度为1.5cps～20cps范围。进一步地，油墨在工作温度或25℃下的粘度为4.0cps～20cps。In one of the embodiments, the viscosity of the ink at an operating temperature or 25 ° C is from 1 cps to 100 cps, and the lower viscosity allows the ink to be suitable for ink jet printing. Further, the viscosity of the ink at an operating temperature or 25 ° C is from 1 cps to 50 cps. Further, the viscosity of the ink at an operating temperature or 25 ° C is in the range of 1.5 cps to 20 cps. Further, the viscosity of the ink at an operating temperature or 25 ° C is from 4.0 cps to 20 cps.
需要说明的是，粘度可以通过不同的方法调节，例如选取合适的溶剂或油墨中功能材料的浓度，其中，功能材料选自含有交联基团的化合物及有机功能材料中的至少一种。在其中一个实施例中，上述油墨能够根据所用的印刷方法调整油墨中的功能材料的浓度。具体地，油墨中的功能材料的含量为0.3wt％～30wt％范围。进一步地，油墨中的功能材料的含量为0.5wt％～20wt％。油墨中的功能材料的含量为0.5wt％～15wt％。油墨中的功能材料的含量为0.5wt％～10wt％。油墨中的功能材料的含量为1wt％～5wt％。It should be noted that the viscosity can be adjusted by different methods, for example, selecting a suitable solvent or a concentration of the functional material in the ink, wherein the functional material is selected from at least one of a compound containing a crosslinking group and an organic functional material. In one of the embodiments, the ink can adjust the concentration of the functional material in the ink according to the printing method used. Specifically, the content of the functional material in the ink is in the range of 0.3% by weight to 30% by weight. Further, the content of the functional material in the ink is from 0.5% by weight to 20% by weight. The content of the functional material in the ink is from 0.5% by weight to 15% by weight. The content of the functional material in the ink is from 0.5% by weight to 10% by weight. The content of the functional material in the ink is from 1% by weight to 5% by weight.
上述油墨用于制备有机电子器件。The above inks are used to prepare organic electronic devices.
在其中一个实施例中，上述油墨用于制备有机电子器件的方法为打印或涂布。In one embodiment, the above method of ink for preparing an organic electronic device is printing or coating.
进一步地，打印或涂布技术包含(但不限于)喷墨打印、喷印(Nozzle Printing)、活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂、移印、喷印刷(Nozzle printing)及狭缝型挤压式涂布。更进一步地，打印或涂布技术包含喷墨印刷、狭缝型挤压式涂布、喷印刷及凹版印刷。Further, printing or coating techniques include, but are not limited to, ink jet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roll printing, torsion roll printing. , lithographic, flexographic, rotary printing, spray coating, brush coating, pad printing, spray printing (Nozzle printing) and slit extrusion coating. Still further, printing or coating techniques include ink jet printing, slit type extrusion coating, jet printing, and gravure printing.
一实施方式的有机功能材料薄膜，包括上述含有交联基团的化合物。A film of an organic functional material according to an embodiment includes the above-mentioned compound containing a crosslinking group.
在其中一个实施例中，有机功能材料薄膜通过溶液加工的方法制备而成。有机功能材料薄膜能够用于有机电子器件中。In one of the embodiments, the organic functional material film is prepared by a solution processing method. Organic functional material films can be used in organic electronic devices.
一实施方式的有机功能材料薄膜的制备方法，包括如下步骤(1)～步骤(4)：A method for preparing an organic functional material film according to an embodiment comprises the following steps (1) to (4):
步骤(1)、制备含有上述含有交联基团的化合物的膜液。Step (1), preparing a membrane liquid containing the above-mentioned compound containing a crosslinking group.
具体地，将包含上述含有交联基团的化合物的有机组分溶于溶剂中，制得溶液。Specifically, a solution containing the above-mentioned organic component containing a crosslinking group-containing compound is dissolved in a solvent.
步骤(2)、将膜液制备成膜层。In step (2), the membrane liquid is prepared into a film layer.
具体地，用印刷或涂布的方法将上述膜液涂布于基板上形成膜层。其中，印刷或涂布的方法可选于，但不限于，喷墨打印、喷印(Nozzle Printing)、活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂、移印及狭缝型挤压式涂布等。Specifically, the above film liquid is applied onto a substrate by a printing or coating method to form a film layer. Wherein, the printing or coating method may be selected from, but not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twisting. Roll printing, lithography, flexographic printing, rotary printing, spray coating, brushing, pad printing and slit-type extrusion coating.
步骤(3)、使膜层中含有交联基团的化合物发生交联反应，得到固化薄膜。In the step (3), a compound having a crosslinking group in the film layer is subjected to a crosslinking reaction to obtain a cured film.
具体地，将含有膜层的基板置于至少100℃下进行加热处理，使膜层中含有交联基团的化合物发生交联反应，得到固化薄膜。需要说明的是，还可以对膜层进行紫外光照，使膜层中含有交联基团的化合物发生交联反应，得到固化薄膜。Specifically, the substrate containing the film layer is subjected to heat treatment at at least 100 ° C to cause a crosslinking reaction of the compound having a crosslinking group in the film layer to obtain a cured film. It should be noted that the film layer may be subjected to ultraviolet light to cause a crosslinking reaction of the compound having a crosslinking group in the film layer to obtain a cured film.
步骤(4)、用有机溶剂清洗固化薄膜，以去除未交联固化的化合物，得到有机功能薄膜。需要说明的是，得到的固化薄膜能够满足实际需求，步骤(4)可以省略。Step (4), the cured film is washed with an organic solvent to remove the uncrosslinked solidified compound to obtain an organic functional film. It should be noted that the obtained cured film can meet the actual needs, and the step (4) can be omitted.
在其中一个实施例中，有机功能薄膜的厚度至少是膜层厚度的50％。进一步地，有机功能薄膜的厚度至少是膜层厚度的60％。进一步地，有机功能薄膜的厚度至少是膜层厚度的70％。进一步地，有机功能薄膜的厚度至少是膜层厚度的85％。In one of the embodiments, the thickness of the organic functional film is at least 50% of the thickness of the film layer. Further, the thickness of the organic functional film is at least 60% of the thickness of the film layer. Further, the thickness of the organic functional film is at least 70% of the thickness of the film layer. Further, the thickness of the organic functional film is at least 85% of the thickness of the film layer.
基于上述化合物，本发明还提供一种如上所述的含有交联基团的化合物在有机电子器件的应用。所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器或有机等离激元发射二极管(Organic Plasmon Emitting Diode)等。进一步地，有机电子器件为OLED。在其中一个实施例中，将所述的含有交联基团的化 合物用于OLED的空穴传输层、空穴注入层或发光层中。进一步地，将所述的含有交联基团的化合物用于OLED的空穴传输层。Based on the above compounds, the present invention also provides the use of a crosslinking group-containing compound as described above in an organic electronic device. The organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode). Further, the organic electronic device is an OLED. In one embodiment, the said crosslinking group-containing group The compound is used in a hole transport layer, a hole injection layer or a light-emitting layer of an OLED. Further, the crosslinking group-containing compound is used for a hole transport layer of an OLED.
进一步地，本发明涉及一种有机电子器件，有机电子器件包含至少一种含有交联基团的化合物。在其中一个实施例中，有机电子器件包括功能层，功能层由上述组合物制备而成。进一步地，有机电子器件至少包含阴极、阳极及位于阴极和阳极之间的功能层，功能层中包含至少一种如上所述的含有交联基团的化合物。Further, the present invention relates to an organic electronic device comprising at least one compound containing a crosslinking group. In one embodiment, the organic electronic device includes a functional layer prepared from the above composition. Further, the organic electronic device comprises at least a cathode, an anode, and a functional layer between the cathode and the anode, and the functional layer contains at least one compound containing a crosslinking group as described above.
在其中一个实施例中，有机电子器件为有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器，有机自旋电子器件、有机传感器或有机等离激元发射二极管(Organic Plasmon Emitting Diode)。In one embodiment, the organic electronic device is an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic Spintronics, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode).
在其中一个实施例中，有机电子器件为电致发光器件。进一步地，如图1所示，有机电子器件为OLED100(如图一所示)，OLED100包括基片101、阳极102、发光层104及阴极106。需要说明的是，OLED100还包括空穴传输层103、电子传输层105。In one of the embodiments, the organic electronic device is an electroluminescent device. Further, as shown in FIG. 1 , the organic electronic device is an OLED 100 (shown in FIG. 1 ), and the OLED 100 includes a substrate 101 , an anode 102 , a light emitting layer 104 , and a cathode 106 . It should be noted that the OLED 100 further includes a hole transport layer 103 and an electron transport layer 105.
基片101为透明基板或不透明基板。透明基板能够用来制造透明的发光元器件，例如可参见，Bulovic等Nature 1996,380,p29、Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料、金属、半导体晶片或玻璃。进一步地，基片有一个平滑的表面，无表面缺陷的基片是特别理想的选择。在其中一个实施例中，柔性的基片可以是聚合物薄膜或塑料。进一步地，基片101的玻璃化温度Tg大于150℃。进一步地，基片101的玻璃化温度Tg大于200℃。进一步地，基片101的玻璃化温度Tg大于250℃。进一步地，基片101的玻璃化温度Tg大于300℃。合适的柔性基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。The substrate 101 is a transparent substrate or an opaque substrate. Transparent substrates can be used to make transparent light-emitting components, see, for example, Bulovic et al. Nature 1996, 380, p29, Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Further, the substrate has a smooth surface, and a substrate having no surface defects is a particularly desirable option. In one embodiment, the flexible substrate can be a polymeric film or plastic. Further, the glass transition temperature Tg of the substrate 101 is greater than 150 °C. Further, the glass transition temperature Tg of the substrate 101 is greater than 200 °C. Further, the glass transition temperature Tg of the substrate 101 is greater than 250 °C. Further, the glass transition temperature Tg of the substrate 101 is more than 300 °C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
阳极(102)为导电金属、金属氧化物或导电聚合物。阳极102可以容易地注入空穴到空穴注入层(HIL)、空穴传输层(HTL)或发光层中。在图示实施方式中，阳极102层叠于基片101的一侧。在其中一个的实施例中，阳极102的功函数和发光层104中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV。进一步地，阳极102的功函数和发光层中的发光体104或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.3eV。进一步地，阳极102的功函数和发光层104中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.2eV。能够作为阳极102的材料的例子包括但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适作为阳极102的材料是已知的，本领域普通技术人员可容易地选择使用。阳极102可以使用任何合适的技术沉积，例如物理气相沉积法，物理气相沉积法包括射频磁控溅射、真空热蒸发、电子束(e-beam)等。在某些实施例中，阳极102是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。The anode (102) is a conductive metal, a metal oxide or a conductive polymer. The anode 102 can easily inject holes into a hole injection layer (HIL), a hole transport layer (HTL), or a light-emitting layer. In the illustrated embodiment, the anode 102 is laminated on one side of the substrate 101. In one of the embodiments, the work function of the anode 102 and the difference between the HOMO level or the valence band level of the illuminant in the luminescent layer 104 or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) The absolute value is less than 0.5 eV. Further, the work function of the anode 102 and the absolute value of the difference between the HOMO level or the valence band level of the illuminant 104 in the luminescent layer or the p-type semiconductor material as the HIL or HTL or the electron blocking layer (EBL) is less than 0.3 eV. . Further, the work function of the anode 102 and the absolute value of the difference between the HOMO level or the valence band level of the illuminant in the luminescent layer 104 or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.2 eV. . Examples of materials that can be used as the anode 102 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 materials for the anode 102 are known and can be readily selected for use by one of ordinary skill in the art. The anode 102 can be deposited using any suitable technique, such as physical vapor deposition, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode 102 is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
阴极106为导电金属或金属氧化物。阴极106可以容易地注入电子到EIL、ETL或发光层104中。在图示实施方式中，阴极106层叠于阳极102远离基片101的一侧。在其中一个的实施例中，阴极106的功函数和发光层中发光体104或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV。进一步地，阴极106的功函数和发光层104中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.3eV。阴极106的功函数和发光层104中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。能够作为阴极106的材料的例子包括但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。能够作为阴极106的材料可以使用任何合适的技术沉积，例如物理气相沉积法，物理气相沉积法包括射频磁控溅射、真空热蒸发、电子束(e-beam)等。 Cathode 106 is a conductive metal or metal oxide. The cathode 106 can easily inject electrons into the EIL, ETL or luminescent layer 104. In the illustrated embodiment, the cathode 106 is laminated on the side of the anode 102 remote from the substrate 101. In one of the embodiments, the work function of the cathode 106 and the LUMO in the light-emitting layer or the LUMO of the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference between the energy level or the conduction band energy level is less than 0.5 eV. Further, the work function of the cathode 106 and the LUMO level or conduction band of the illuminant in the luminescent layer 104 or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference in energy levels is less than 0.3 eV. The work function of the cathode 106 and the LUMO level or conduction band level of the illuminant in the luminescent layer 104 or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference is less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of materials that can be used as the cathode 106 include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The material capable of functioning as the cathode 106 can be deposited using any suitable technique, such as physical vapor deposition, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
在图示实施方式中，发光层104层叠于阳极102远离基片101的一侧，且位于阴极106靠近阳极102的一侧。在其中一个的实施例中，发光层104由上述含有交联基团的组合物制 备而成。具体地，发光层104是通过打印上述组合物制备而成。In the illustrated embodiment, the luminescent layer 104 is layered on the side of the anode 102 remote from the substrate 101 and on the side of the cathode 106 adjacent the anode 102. In one embodiment, the light-emitting layer 104 is made of the above-described composition containing a crosslinking group. Prepared. Specifically, the light-emitting layer 104 is prepared by printing the above composition.
需要说明的是，OLED100还可以包含其他功能层，如空穴注入层(HIL)、空穴传输层103(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层105(ETL)或空穴阻挡层(HBL)。适合用于这些功能层中的材料在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本实施方式作为参考。在图示实施方式中，空穴传输层103层叠于阳极102远离基片101的一侧，且位于发光层104靠近阳极102的一侧。电子传输层105层叠于发光层104远离空穴传输层103的一侧，且位于阴极106靠近发光层104的一侧。It should be noted that the OLED 100 may further include other functional layers such as a hole injection layer (HIL), a hole transport layer 103 (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), and an electron transport layer 105 ( ETL) or a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of each of each of In the illustrated embodiment, the hole transport layer 103 is laminated on the side of the anode 102 remote from the substrate 101 and on the side of the luminescent layer 104 that is adjacent to the anode 102. The electron transport layer 105 is laminated on the side of the light emitting layer 104 away from the hole transport layer 103 and on the side of the cathode 106 close to the light emitting layer 104.
在其中一个的实施例中，空穴传输层103由上述含有交联基团的组合物制备而成。In one of the embodiments, the hole transport layer 103 is prepared from the above composition containing a crosslinking group.
在其中一个的实施例中，上述电子发光器件的发光波长为300nm～1000nm。进一步地，上述电子发光器件的发光波长为350nm～900nm。进一步地，上述电子发光器件的发光波长为400nm～800nm。In one embodiment, the electron-emitting device has an emission wavelength of 300 nm to 1000 nm. Further, the above-described electron light-emitting device has an emission wavelength of 350 nm to 900 nm. Further, the above-described electron light-emitting device has an emission wavelength of 400 nm to 800 nm.
上述有机电子器件在各种电子设备中的应用。在其中一个实施例中，电子设备为显示设备、照明设备、光源或传感器。需要说明的是，电子设备不限于上述设备，还可以包括其他电子设备。The above-mentioned organic electronic device is used in various electronic devices. In one of these embodiments, the electronic device is a display device, a lighting device, a light source, or a sensor. It should be noted that the electronic device is not limited to the above device, and may also include other electronic devices.
以下为具体实施例部分：The following are specific examples:
实施例1：化合物1(即HTM1)的合成：Example 1: Synthesis of Compound 1 (ie, HTM1):
Figure PCTCN2017118065-appb-000040
Figure PCTCN2017118065-appb-000040
室温下依次将13.6g(0.018mol)的中间体a和9.19g(0.018mol)的中间体b溶于300mL的甲苯中，依次加入四三苯基膦钯1.2g、碳酸钾10g(0.74mol)、水60mL、乙醇60mL，加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后将有机相干燥浓缩得到粗品，经层析柱纯化后的固体为化合物1，得到的化合物1为13.0g，收率为68％。13.6 g (0.018 mol) of the intermediate a and 9.19 g (0.018 mol) of the intermediate b were successively dissolved in 300 mL of toluene at room temperature, followed by the addition of 1.2 g of tetrakistriphenylphosphine palladium and 10 g of potassium carbonate (0.74 mol). 60 mL of water and 60 mL of ethanol were heated to 110 ° C for 15 hours, and the TLC plate showed complete reaction. The reaction solution was added to water and extracted with dichloromethane three times, and then the organic phase was dried and concentrated to give a crude product. The solid purified by chromatography column was Compound 1 and the compound 1 obtained was 13.0 g, yield 68%.
实施例2：化合物2(即HTM2)的合成Example 2: Synthesis of Compound 2 (ie, HTM2)
Figure PCTCN2017118065-appb-000041
Figure PCTCN2017118065-appb-000041
室温下依次将13.6g(0.018mol)的中间体a和13.3g(0.018mol)的中间体b溶于300mL的甲苯中，依次加入四三苯基膦钯1.2g、碳酸钾9.7g(0.074mol)、水60mL、乙醇60mL，加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后将有机相干燥浓缩得到粗品，经层析柱纯化后的固体为化合物2，得到的化合物1为15.1g，收率为65％。13.6 g (0.018 mol) of the intermediate a and 13.3 g (0.018 mol) of the intermediate b were successively dissolved in 300 mL of toluene at room temperature, and then 1.2 g of tetrakistriphenylphosphine palladium and 9.7 g of potassium carbonate (0.074 mol) were sequentially added. ), 60 mL of water and 60 mL of ethanol were heated to 110 ° C for 15 hours, and the TLC plate showed complete reaction. The reaction solution was added to water and extracted with dichloromethane three times, then the organic phase was dried and concentrated to give a crude product. The solid purified by chromatography column was Compound 2, and the compound 1 obtained was 15.1 g, and the yield was 65%.
实施例3：化合物3(即HTM3)的合成 Example 3: Synthesis of Compound 3 (ie, HTM3)
Figure PCTCN2017118065-appb-000042
Figure PCTCN2017118065-appb-000042
将5.0mmol中间体a溶解于200mL干燥的四氢呋喃(THF)溶液中，氮气环境保护下，反应液置于-78℃的温度下搅拌，逐滴加入8.0mmol的亚甲基三苯基磷(Wittig试剂)，待加入完毕后，逐渐升至室温，继续在室温下搅拌过夜，加水淬灭反应，所有反应液用二氯甲烷萃取，有机相用水洗涤，最后合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，所得产物用硅胶柱纯化，流动相为二氯甲烷：石油醚＝1:2，最后得到3.5mmol的化合物3。真空环境下干燥待用。其中，化合物3的MS(APCI)为754.0。5.0 mmol of the intermediate a was dissolved in 200 mL of a dry tetrahydrofuran (THF) solution, and the reaction solution was stirred at a temperature of -78 ° C under nitrogen atmosphere, and 8.0 mmol of methylenetriphenylphosphorus (Wittig) was added dropwise. Reagents, after the addition, gradually increase to room temperature, continue to stir at room temperature overnight, quench the reaction with water, all the reaction mixture is extracted with dichloromethane, the organic phase is washed with water, and the organic phase is combined and dried over anhydrous sodium sulfate The organic solvent was evaporated to dryness, and the obtained product was purified on silica gel column, methylene chloride: petroleum ether = 1:2, and finally 3.5 mmol of compound 3. Dry in a vacuum environment for use. Among them, the MS (APCI) of Compound 3 was 754.0.
实施例4：化合物4(即HTM4)的合成Example 4: Synthesis of Compound 4 (ie HTM4)
Figure PCTCN2017118065-appb-000043
Figure PCTCN2017118065-appb-000043
将5.0mmol中间体a溶解于200mL干燥的四氢呋喃(THF)溶液中，氮气环境保护下，反应液置于-78℃的温度下搅拌，逐滴加入8.0mmol的亚甲基三苯基磷(Wittig试剂)，待加入完毕后，逐渐升至室温，继续在室温下搅拌过夜，加水淬灭反应，所有反应液用二氯甲烷萃取，有机相用水洗涤，最后合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，所得产物用硅胶柱纯化，流动相为二氯甲烷：石油醚＝1:2，最后得到3.9mmol的化合物4。真空环境下干燥待用。其中，化合物4的MS(APCI)为754.0。5.0 mmol of the intermediate a was dissolved in 200 mL of a dry tetrahydrofuran (THF) solution, and the reaction solution was stirred at a temperature of -78 ° C under nitrogen atmosphere, and 8.0 mmol of methylenetriphenylphosphorus (Wittig) was added dropwise. Reagents, after the addition, gradually increase to room temperature, continue to stir at room temperature overnight, quench the reaction with water, all the reaction mixture is extracted with dichloromethane, the organic phase is washed with water, and the organic phase is combined and dried over anhydrous sodium sulfate The organic solvent was evaporated to dryness. The obtained product was purified on silica gel column eluting with methylene chloride: petroleum ether = 1:2. Dry in a vacuum environment for use. Among them, the MS (APCI) of Compound 4 was 754.0.
实施例5：化合物5(即HTM5)的合成Example 5: Synthesis of Compound 5 (ie HTM5)
Figure PCTCN2017118065-appb-000044
Figure PCTCN2017118065-appb-000044
将5.0mmol中间体a溶解于200mL干燥的四氢呋喃(THF)溶液中，氮气环境保护下，反应液置于-78℃的温度下搅拌，逐滴加入8.0mmol的亚甲基三苯基磷(Wittig试剂)，待加入完毕后，逐渐升至室温，继续在室温下搅拌过夜，加水淬灭反应，所有反应液用二氯甲烷萃取，有机相用水洗涤，最后合并有机相，用无水硫酸钠干燥，过滤，蒸干有机溶剂，所得产物用硅胶柱纯化，流动相为二氯甲烷：石油醚＝1:2，最后得到3.0mmol化合物5。真空环境下干燥待用。其中，化合物5的MS(APCI)为1023.3。5.0 mmol of the intermediate a was dissolved in 200 mL of a dry tetrahydrofuran (THF) solution, and the reaction solution was stirred at a temperature of -78 ° C under nitrogen atmosphere, and 8.0 mmol of methylenetriphenylphosphorus (Wittig) was added dropwise. Reagents, after the addition, gradually increase to room temperature, continue to stir at room temperature overnight, quench the reaction with water, all the reaction mixture is extracted with dichloromethane, the organic phase is washed with water, and the organic phase is combined and dried over anhydrous sodium sulfate The organic solvent was evaporated to dryness, and the obtained product was purified on silica gel column, methylene chloride: petroleum ether = 1:2, and finally, Dry in a vacuum environment for use. Among them, the MS (APCI) of Compound 5 was 1023.3.
测试：test:
1、能量结构进行测定1. Determination of energy structure
化合物的能级利用TD-DFT(含时密度泛函理论)通过Gaussian09W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。具体地，用密度函数方法“Ground State/DFT/Default  Spin/B3LYP”与基组“6-31G(d)”(Charge 0/Spin Singlet)来优化化合物的几何结构，化合物的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91”与基组“6-31G(d)”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式(1)和(2)计算，S1和T1直接使用。The energy level of the compound is determined by TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. Specifically, use the density function method "Ground State/DFT/Default Spin/B3LYP" and the base group "6-31G(d)" (Charge 0/Spin Singlet) are used to optimize the geometry of the compound. The energy structure of the compound is calculated by the TD-DFT (time-dependent density functional theory) method. SCF/DFT/Default Spin/B3PW91" and base group "6-31G(d)" (Charge 0/Spin Singlet). HOMO and LUMO energy levels are calculated according to the following calibration formulas (1) and (2), S1 and T1 Use directly.
HOMO(eV)＝[(HOMO(G)×27.212)-0.9899]/1.1206校准公式(1)，HOMO(eV)=[(HOMO(G)×27.212)-0.9899]/1.1206 calibration formula (1),
其中，HOMO(G)通过Gaussian 03W的直接计算结果，单位为Hartree；Among them, HOMO(G) is directly calculated by Gaussian 03W, and the unit is Hartree;
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385校准公式(2)，LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385 calibration formula (2),
其中，LUMO(G)通过Gaussian 03W的直接计算结果，单位为Hartree。Among them, LUMO(G) is directly calculated by Gaussian 03W, and the unit is Hartree.
NPB为标准材料，NPB的结构式为：NPB is a standard material, and the structural formula of NPB is:
Figure PCTCN2017118065-appb-000045
Figure PCTCN2017118065-appb-000045
分别测定实施例1～5的化合物及的HOMO能级、LUMO能级、T1能级及S1能级The compounds of Examples 1 to 5 and the HOMO level, LUMO level, T 1 level and S 1 level were measured, respectively.
表1 能级结构Table 1 Energy level structure
  HOMO[eV]HOMO[eV] LUMO[eV]LUMO[eV] T1[eV]T 1 [eV] S1[eV]S 1 [eV]
实施例1Example 1 -5.16-5.16 -2.17-2.17 2.602.60 3.103.10
实施例2Example 2 -5.17-5.17 -2.17-2.17 2.612.61 3.153.15
实施例3Example 3 -5.14-5.14 -2.25-2.25 2.472.47 3.203.20
实施例4Example 4 -5.26-5.26 -2.19-2.19 2.592.59 3.223.22
实施例5Example 5 -5.21-5.21 -2.28-2.28 2.582.58 3.203.20
NPBNPB -5.18-5.18 -2.34-2.34 2.442.44 3.073.07
由表2可以看出，实施例1～5的化合物的HOMO与LUMO的能级差较小，说明实施例1～5的化合物的稳定性较好，同时，实施例1～5的化合物的ΔEST[即Δ(S1-T1)，单线态能级与三线态能级之间的能级差]均较小，说明包括实施例1～5的化合物的材料的发光效率较高。As can be seen from Table 2, the compounds of Examples 1 to 5 have a small difference in energy level between HOMO and LUMO, indicating that the compounds of Examples 1 to 5 have good stability, and at the same time, the ΔE ST of the compounds of Examples 1 to 5 [i.e., Δ(S 1 -T 1 ), the energy level difference between the singlet energy level and the triplet energy level] is small, indicating that the materials including the compounds of Examples 1 to 5 have high luminous efficiency.
2、实施例1～5的化合物及Poly-TFB(即Poly-Trifluroboran)作为空穴传输层的材料对OLED的寿命的影响。2. The effect of the compounds of Examples 1 to 5 and Poly-TFB (i.e., Poly-Trifluroboran) as a material of the hole transport layer on the lifetime of the OLED.
发光层的材料如下：The materials of the luminescent layer are as follows:
Figure PCTCN2017118065-appb-000046
Figure PCTCN2017118065-appb-000046
其中，H1是共主体材料，其合成参照申请号为CN201510889328.8的中国专利；H2是共主体材料，其合成参照专利WO201034125A1；E1是磷光辅助材料，其合成参照专利CN102668152；Wherein, H1 is a co-host material, and its synthesis is referred to the Chinese patent of application number CN201510889328.8; H2 is a co-host material, and its synthesis is referred to the patent WO201034125A1; E1 is a phosphorescent auxiliary material, and its synthesis is referred to the patent CN102668152;
OLED器件制备步骤如下：The OLED device preparation steps are as follows:
1)ITO透明电极(阳极)玻璃衬底的清洗：使用含有5％Decon90清洗液的水溶液对ITO透明电极玻璃衬底超声处理30分钟，然后去离子水超声清洗3次，然后异丙醇超声清洗15分钟，氮气吹干；在氧气等离子下处理5分钟，以清洁ITO透明电极玻璃衬底表面并提升ITO透明电极的功函数；1) ITO transparent electrode (anode) glass substrate cleaning: ITO transparent electrode glass substrate was sonicated for 30 minutes using an aqueous solution containing 5% Decon 90 cleaning solution, then ultrasonically cleaned 3 times with deionized water, followed by ultrasonic cleaning with isopropanol 15 minutes, nitrogen drying; treatment under oxygen plasma for 5 minutes to clean the surface of the ITO transparent electrode glass substrate and enhance the work function of the ITO transparent electrode;
2)HIL及HTL的制备:在经过氧气等离子体处理过的玻璃衬底上旋涂PEDOT:PSS(CleviosTMPEDOT:PSS Al4083)，，得到80nm的薄膜，旋涂完成后在空气中150℃退火20分钟，然后在PEDOT:PSS层上旋涂得HTL层的材料，得到到20nm的HTL层，随后在180℃ 的热板上处理60分钟；2) Preparation of HIL and HTL: PEDOT:PSS (Clevios TM PEDOT:PSS Al4083) was spin-coated on an oxygen plasma-treated glass substrate to obtain a film of 80 nm, which was annealed at 150 ° C in air after spin coating. After 20 minutes, the material of the HTL layer was spin-coated on the PEDOT:PSS layer to obtain a 20 nm HTL layer, followed by treatment on a hot plate at 180 ° C for 60 minutes;
3)发光层制备:先将H1、H2、E1按照40：40：20的重量比例溶于甲苯中，溶液的浓度为20mg/mL，将此溶液在氮气手套箱中旋涂得到60nm薄膜，然后在120℃退火10分钟。3) Preparation of luminescent layer: firstly dissolve H1, H2, E1 in toluene according to the weight ratio of 40:40:20, the concentration of the solution is 20 mg/mL, spin the solution in a nitrogen glove box to obtain a 60 nm film, and then Annealed at 120 ° C for 10 minutes.
4)阴极制备：将旋涂完成的器件放入真空蒸镀腔体，依次蒸镀2nm的钡和100nm的铝，得到OLED。4) Cathode preparation: The spin-coated device was placed in a vacuum evaporation chamber, and 2 nm of ruthenium and 100 nm of aluminum were sequentially evaporated to obtain an OLED.
5)将器件置于氮气手套箱中，采用紫外固化树脂加玻璃盖板封装。5) Place the device in a nitrogen glove box and enclose it with a UV-curable resin and a glass cover.
其中，在HTL层制备时，HTL层的材料分别为Poly-TFB(CAS:223569-31-1，购自Lumtec.Corp；5mg/mL甲苯溶液)、实施例1～5的化合物。其中，使用实施例1～5的化合物作为HTL层的材料时，测定HTL层的厚度前，用甲苯将HTL层冲洗两次。Among them, in the preparation of the HTL layer, the materials of the HTL layer were Poly-TFB (CAS: 223569-31-1, available from Lumtec. Corp; 5 mg/mL toluene solution), and the compounds of Examples 1 to 5, respectively. Here, when the compounds of Examples 1 to 5 were used as the material of the HTL layer, the HTL layer was washed twice with toluene before measuring the thickness of the HTL layer.
器件的电流-电压特性和外量子效率由Keithley236电流电压-测量***及一个经校正的硅光二极管测得。其中，含有实施例1～5的化合物的OLED的外量子效率为含有Poly-TFB的OLED的外量子效率的相对值。结果详见表2。The current-voltage characteristics and external quantum efficiency of the device were measured by a Keithley 236 current-voltage-measurement system and a calibrated silicon photodiode. Among them, the external quantum efficiency of the OLED containing the compounds of Examples 1 to 5 is a relative value of the external quantum efficiency of the OLED containing Poly-TFB. The results are shown in Table 2.
表2 OLED的HTL的厚度及外量子效率Table 2 Thickness and External Quantum Efficiency of HTL of OLED
化合物Compound HTL厚度(nm)HTL thickness (nm) 外量子效率(cd/A)@1000nitsExternal quantum efficiency (cd/A) @1000nits
Poly-TFBPoly-TFB 2020 11
HTM1HTM1 1313 1.811.81
HTM2HTM2 1212 1.551.55
HTM3HTM3 1515 1.741.74
HTM4HTM4 1717 2.122.12
HTM5HTM5 1616 1.431.43
由表2可以看出，含有实施例1～5的化合物的OLED的外量子效率均至少为含有Poly-TFB的OLED的外量子效率的1.43倍。说明实施例1～5的化合物更有利提高OLED的性能，可能是由于实施例1～5的化合物中含有可交联小分子，使得这些化合物具有较高的三线态能级，从而对三线态有了较好的阻挡作用。As can be seen from Table 2, the external quantum efficiency of the OLEDs containing the compounds of Examples 1 to 5 was at least 1.43 times the external quantum efficiency of the OLED containing Poly-TFB. It is explained that the compounds of Examples 1 to 5 are more advantageous for improving the performance of the OLED, possibly because the compounds of Examples 1 to 5 contain crosslinkable small molecules, so that these compounds have a higher triplet energy level, thereby having a triplet state. A better blocking effect.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (16)

  1. 一种含有交联基团的化合物，其特征在于，具有如下结构式(I)：A compound containing a crosslinking group characterized by having the following structural formula (I):
    Figure PCTCN2017118065-appb-100001
    Figure PCTCN2017118065-appb-100001
    其中，SG具有结构式(II)：Among them, SG has the structural formula (II):
    Figure PCTCN2017118065-appb-100002
    Figure PCTCN2017118065-appb-100002
    Ar为环原子数为5～20的芳基或环原子数为5～20的杂芳基；Ar is an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 20 ring atoms;
    CLG为交联基团；CLG is a crosslinking group;
    o为0或1；o is 0 or 1;
    p为大于或等于2的整数；p is an integer greater than or equal to 2;
    A的结构式III为：The structural formula III of A is:
    Figure PCTCN2017118065-appb-100003
    Figure PCTCN2017118065-appb-100003
    其中，R1为F、Cl、Br、I、D、CN、NO2、CF3、B(OR2)2、Si(R2)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃基，R2为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳族或环原子数为5～10的杂芳族基团，Wherein R 1 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , a linear alkane having 1 to 10 carbon atoms, and total An alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having 3 to 10 total carbon atoms, and a cycloalkane group having 3 to 10 total carbon atoms; R 2 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aromatic group having 5 to 10 ring atoms or a heteroaromatic group having 5 to 10 ring atoms.
    -L-为单键或碳原子数为5～40芳族基团，-L- is a single bond or a carbon atom having 5 to 40 aromatic groups,
    Ar1为环原子数为5～40的芳族基团或环原子数为5～40的杂芳族基团，Ar 1 is an aromatic group having 5 to 40 ring atoms or a heteroaromatic group having 5 to 40 ring atoms.
    y为0～5的整数，Y is an integer from 0 to 5,
    Ar0选自如下结构式中的一种：Ar 0 is selected from one of the following structural formulae:
    Figure PCTCN2017118065-appb-100004
    Figure PCTCN2017118065-appb-100004
    其中，Ar2为环原子数为5～40的芳族基或环原子数为5～40的杂芳族基，Wherein Ar 2 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
    X为0～4的整数，X1为0～3的整数，X is an integer from 0 to 4, and X1 is an integer from 0 to 3.
    -Z-不存在或为单键及二桥联基中的一种，-Z- does not exist or is one of a single bond and a two bridged base,
    m选自0～10的整数，m is selected from an integer of 0 to 10,
    R9为F、Cl、Br、I、D、CN、NO2、CF3、B(OR14)2、Si(R14)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃，R14为H、D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳族或环原子数为5～10的杂芳族基团；R 9 is F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 14 ) 2 , Si(R 14 ) 3 , a linear alkane having 1 to 10 carbon atoms, and a total carbon atom. The number is from 1 to 10, an alkane ether, an alkane sulfide having a total carbon number of from 1 to 10, a branched alkane having a total carbon number of from 3 to 10, a cycloalkane having a total carbon number of from 3 to 10, and R 14 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aromatic group having 5 to 10 ring atoms or a heteroaromatic group having 5 to 10 ring atoms;
    所述结构式III中的虚线表示所述L与所述Ar0连接，所述结构式(IIIa)中的虚线和圆圈表示所述L能够与圆圈中两个苯环的任意碳原子或Ar2的结构式中包含的芳香环或杂芳环的任意碳原子连接，所述结构式(IIIb)及所述结构式(IIIc)中的虚线均表示所述L能够连接在虚线穿过的苯环的任意碳原子上。The broken line in the structural formula III indicates that the L is bonded to the Ar 0 , and the dotted line and the circle in the structural formula (IIIa) indicate that the L can be combined with any carbon atom or Ar 2 of two benzene rings in the circle. Any of the carbon atoms contained in the aromatic ring or the heteroaryl ring is bonded, and the broken lines in the structural formula (IIIb) and the structural formula (IIIc) each indicate that the L can be attached to any carbon atom of the benzene ring through which the broken line passes. .
  2. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述Ar选自如下结构 式中的一种：The crosslinking group-containing compound according to claim 1, wherein the Ar is selected from the following structures One of the formulas:
    Figure PCTCN2017118065-appb-100005
    Figure PCTCN2017118065-appb-100006
    及
    Figure PCTCN2017118065-appb-100007
    Figure PCTCN2017118065-appb-100005
    Figure PCTCN2017118065-appb-100006
    and
    Figure PCTCN2017118065-appb-100007
    其中，X2为C-R15或N，Where X 2 is CR 15 or N,
    Y2为C-R16-R17、Si-R18-R19、N-R20、C(＝O)、S(＝O)2、O或S，Y 2 is CR 16 -R 17 , Si-R 18 -R 19 , NR 20 , C(=O), S(=O) 2, O or S,
    -R15、-R16、-R17、-R18、-R19及-R20分别独立选自为H、D、F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠环芳基、碳原子数为4～60的稠杂环芳基及上述基团中至少两个相互连接形成的组合基团中的一种。-R 15 , -R 16 , -R 17 , -R 18 , -R 19 and -R 20 are each independently selected from the group consisting of H, D, F, -CN, -NO 2 , -CF 3 , alkenyl, alkynyl , an amine group, an acyl group, an amide group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, carbon An aryl group having 6 to 60 atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused ring aryl group having 7 to 60 carbon atoms, a fused heterocyclic aryl group having 4 to 60 carbon atoms, and the above One of the combination groups formed by at least two interconnections in the group.
  3. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述CLG为环状单烯基、线状单烯基、线状二烯基、炔基、烯氧基、二烯氧基、丙烯酸基、环氧丙烷基、环氧乙烷基、硅烷基或环丁烷基。The crosslinking group-containing compound according to claim 1, wherein the CLG is a cyclic monoalkenyl group, a linear monoalkenyl group, a linear dienyl group, an alkynyl group, an alkenyloxy group, and a diene. Alkoxy, acrylate, propylene oxide, oxiranyl, silane or cyclobutane.
  4. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述CLG选自如下基团中的一种：The crosslinking group-containing compound according to claim 1, wherein the CLG is selected from one of the following groups:
    Figure PCTCN2017118065-appb-100008
    Figure PCTCN2017118065-appb-100009
    Figure PCTCN2017118065-appb-100010
    及
    Figure PCTCN2017118065-appb-100011
    Figure PCTCN2017118065-appb-100008
    Figure PCTCN2017118065-appb-100009
    Figure PCTCN2017118065-appb-100010
    and
    Figure PCTCN2017118065-appb-100011
    其中，R10、R11、R12及R13分别独立选自F、Cl、Br、I、D、CN、NO2、CF3、B(OR21)2、Si(R21)3、碳原子数为1～10的直链烷烃、总碳原子数为1～10的烷烃醚、总碳原子数为1～10的烷烃硫醚、总碳原子数为3～10的支链烷烃、总碳原子数为3～10的环烷烃、含有总碳原子数为3～10的烷烃醚的基团及含有总碳原子数为3～10的烷烃硫醚的基团中的一种，R21为H、 D、碳原子数为1～10的脂肪族烷烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；Wherein R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 21 ) 2 , Si(R 21 ) 3 , carbon a linear alkane having 1 to 10 atoms, an alkane ether having 1 to 10 carbon atoms, an alkane sulfide having a total carbon number of 1 to 10, a branched alkane having a total carbon number of 3 to 10, and total One of a cycloalkane having 3 to 10 carbon atoms, a group having an alkane ether having 3 to 10 total carbon atoms, and a group having an alkane sulfide having 3 to 10 total carbon atoms, R 21 And H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
    Ar12为环原子数为5～40的芳族基或环原子数为5～40的杂芳基；Ar 12 is an aromatic group having 5 to 40 ring atoms or a heteroaryl group having 5 to 40 ring atoms;
    s为大于等于0的整数，t为大于等于0的整数；s is an integer greater than or equal to 0, and t is an integer greater than or equal to 0;
    上述结构式中的虚线表示所述CLG与其他基团的连接。The dotted line in the above structural formula indicates the connection of the CLG to other groups.
  5. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述L、所述Ar1及所述Ar2分别独立选自如下基团的一种：The crosslinking group-containing compound according to claim 1, wherein the L, the Ar 1 and the Ar 2 are each independently selected from one of the following groups:
    Figure PCTCN2017118065-appb-100012
    Figure PCTCN2017118065-appb-100013
    及
    Figure PCTCN2017118065-appb-100014
    Figure PCTCN2017118065-appb-100012
    Figure PCTCN2017118065-appb-100013
    and
    Figure PCTCN2017118065-appb-100014
    其中，X5为C-R30或N，Where X 5 is CR 30 or N,
    Y5为C-R31-R32、Si-R33-R34、N-R35、C(＝O)、S(＝O)2、O或S，Y 5 is CR 31 -R 32 , Si-R 33 -R 34 , NR 35 , C(=O), S(=O) 2, O or S,
    所述-R30、所述-R31、所述-R32、所述-R33、所述-R34及所述-R35分别独立选自为H、D、F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠环芳基、碳原子数为4～60的稠杂环芳基及上述基团中至少两个相互连接形成的组合基团中的一种。The -R 30 , the -R 31 , the -R 32 , the -R 33 , the -R 34 and the -R 35 are each independently selected from the group consisting of H, D, F, -CN, - NO 2 , -CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone group, alkyl group having 1 to 60 carbon atoms, carbon a cycloalkyl group having 3 to 60 atoms, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused ring aryl group having 7 to 60 carbon atoms, and a carbon number It is a fused heterocyclic aryl group of 4 to 60 and one of the combination groups formed by at least two of the above groups being bonded to each other.
  6. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述L、所述Ar1及所述Ar2分别独立选自如下结构式的一种：The crosslinking group-containing compound according to claim 1, wherein the L, the Ar 1 and the Ar 2 are each independently selected from one of the following structural formulae:
    Figure PCTCN2017118065-appb-100015
    Figure PCTCN2017118065-appb-100016
    Figure PCTCN2017118065-appb-100015
    Figure PCTCN2017118065-appb-100016
    其中，-R3选自-H、-F、-Cl、-Br、-I、-D、-CN、-NO2、-CF3、B(OR40)2、Si(R40)3、直链烷烃、烷烃醚、碳原子数为1～10的烷烃硫醚、支链烷烃、环烷烃、碳原子为3～10的烷烃醚、碳原子数为6～10的芳基中的一种，R40为H、D、碳原子数为1～10的脂肪族烷 烃基、环原子数为5～10的芳基或环原子数为5～10的杂芳基；Wherein -R 3 is selected from the group consisting of -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , B(OR 40 ) 2 , Si(R 40 ) 3 , a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane, an alkane ether having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 40 is H, D, an aliphatic alkane group having 1 to 10 carbon atoms, an aryl group having 5 to 10 ring atoms or a heteroaryl group having 5 to 10 ring atoms;
    u选自0～2的整数中的一个，v选自0～3的整数中的一个，w选自0～4的整数中的一个，t选自0～5的整数中的一个，所述结构式中的虚线表示所述结构式与其他基团的连接。u is selected from one of integers from 0 to 2, v is selected from one of integers from 0 to 3, w is selected from one of integers from 0 to 4, and t is selected from one of integers from 0 to 5, The dashed line in the structural formula indicates the connection of the structural formula to other groups.
  7. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述A的结构式选自如下结构式的一种：The crosslinking group-containing compound according to claim 1, wherein the structural formula of A is selected from one of the following structural formulae:
    Figure PCTCN2017118065-appb-100017
    Figure PCTCN2017118065-appb-100017
  8. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述SG选自如下结构式中的一种：The crosslinking group-containing compound according to claim 1, wherein the SG is selected from one of the following structural formulae:
    Figure PCTCN2017118065-appb-100018
    Figure PCTCN2017118065-appb-100019
    Figure PCTCN2017118065-appb-100020
    及
    Figure PCTCN2017118065-appb-100021
    Figure PCTCN2017118065-appb-100018
    Figure PCTCN2017118065-appb-100019
    Figure PCTCN2017118065-appb-100020
    and
    Figure PCTCN2017118065-appb-100021
    其中，R8选自碳原子数为1～20的直链烷基、碳原子数为1～20的烷氧基、碳原子数为1～20的硫代烷氧基、碳原子数为3～20的支链烷基、碳原子数为3～20的环状烷基、碳原子数为3～20的烷氧基、碳原子数为3～20的硫代烷氧基、碳原子数为3～20的甲硅烷基、碳原子数为1～20的酮基、碳原子数为2～20的烷氧基羰基、碳原子数为7～20的芳氧基羰基、氰基、氨基甲酰基、卤甲酰基、甲酰基、异氰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、硝基、CF3、Cl、Br、F、可交联的基团、碳原子数为5～40的芳基、碳原子数为5～40的杂芳基、碳原子数为5～40的芳氧基、碳原子数为5～40的杂芳氧基及上述基团中至少两个相互连接形成的组合基团；Wherein R 8 is selected from a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms; a branched alkyl group of ～20, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a thioalkoxy group having 3 to 20 carbon atoms, and a carbon number a silyl group of 3 to 20, a ketone group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group or an amino group. Formyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF 3 , Cl, Br, F, crosslinkable groups An aryl group having 5 to 40 carbon atoms, a heteroaryl group having 5 to 40 carbon atoms, an aryloxy group having 5 to 40 carbon atoms, a heteroaryloxy group having 5 to 40 carbon atoms, and the above a combination of at least two groups formed in the group;
    n为大于0的整数；n is an integer greater than 0;
    -L1-表示单键或连接基团；-L 1 - represents a single bond or a linking group;
    上述结构式中的虚线表示所述SG与其他基团的连接。 The dotted line in the above structural formula indicates the connection of the SG to other groups.
  9. 根据权利要求8所述的含有交联基团的化合物，其特征在于，所述L1选自如下结构式中的一种：The crosslinking group-containing compound according to claim 8, wherein the L 1 is selected from one of the following structural formulae:
    Figure PCTCN2017118065-appb-100022
    Figure PCTCN2017118065-appb-100023
    及
    Figure PCTCN2017118065-appb-100024
    上述结构式中的虚线表示所述L1与其他基团的连接。
    Figure PCTCN2017118065-appb-100022
    Figure PCTCN2017118065-appb-100023
    and
    Figure PCTCN2017118065-appb-100024
    The dotted line in the above structural formula indicates the connection of the L 1 to other groups.
  10. 根据权利要求1所述的含有交联基团的化合物，其特征在于，所述含有交联基团的化合物能够在100℃以上发生交联反应。The crosslinking group-containing compound according to claim 1, wherein the crosslinking group-containing compound is capable of undergoing a crosslinking reaction at 100 ° C or higher.
  11. 一种混合物，其特征在于，包括权利要求1～10任一项所述的含有交联基团的化合物及有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料、电子阻挡材料、有机基质材料、单重态发光体、三重态发光体、热激发延迟荧光材料及有机染料中的至少一种。A mixture comprising the crosslinking group-containing compound according to any one of claims 1 to 10, and an organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, and an empty At least one of a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, an organic matrix material, a singlet illuminant, a triplet illuminant, a thermally excited delayed fluorescent material, and an organic dye.
  12. 一种组合物，其特征在于，包括权利要求1～10任一项所述的含有交联基团的化合物及权利要求11所述的混合物中的一种、有机溶剂，所述有机溶剂选自芳族溶剂、芳杂族溶剂、酮类溶剂、醚类溶剂及酯类溶剂中的至少一种。A composition comprising one of the compound containing a crosslinking group according to any one of claims 1 to 10 and the mixture according to claim 11, an organic solvent selected from the group consisting of an organic solvent selected from the group consisting of At least one of an aromatic solvent, an aromatic heterogeneous solvent, a ketone solvent, an ether solvent, and an ester solvent.
  13. 权利要求1～10任一项所述的含有交联基团的化合物、权利要求11所述的混合物及权利要求12所述的组合物中的至少一种制备得到的有机功能薄膜。The organic functional film prepared by at least one of the crosslinking group-containing compound according to any one of claims 1 to 10, the mixture according to claim 11, and the composition according to claim 12.
  14. 一种有机功能薄膜的制备方法，其特征在于，包括如下步骤：A method for preparing an organic functional film, comprising the steps of:
    制备含有权利要求1～10任一项所述的含有交联基团的化合物的膜液；Preparing a membrane liquid containing the crosslinking group-containing compound according to any one of claims 1 to 10;
    将所述膜液制备成膜层；及Preparing the film solution into a film layer; and
    使膜层中所述含有交联基团的化合物发生交联反应，得到有机功能薄膜。The crosslinking group-containing compound in the film layer is subjected to a crosslinking reaction to obtain an organic functional film.
  15. 一种有机电子器件，其特征在于，包括权利要求1～10任一项所述的含有交联基团的化合物。An organic electronic device comprising the crosslinking group-containing compound according to any one of claims 1 to 10.
  16. 根据权利要求15所述的有机电子器件，其特征在于，所述有机电子器件为机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器，有机自旋电子器件、有机传感器或有机等离激元发射二极管。 The organic electronic device according to claim 15, wherein the organic electronic device is a machine light emitting diode, an organic photovoltaic cell, an organic light emitting battery, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, and an organic spin. Electronic device, organic sensor or organic plasmon emitting diode.
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