WO2021027172A1 - 空穴传输材料及其制备方法、有机电致发光器件 - Google Patents

空穴传输材料及其制备方法、有机电致发光器件 Download PDF

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WO2021027172A1
WO2021027172A1 PCT/CN2019/119541 CN2019119541W WO2021027172A1 WO 2021027172 A1 WO2021027172 A1 WO 2021027172A1 CN 2019119541 W CN2019119541 W CN 2019119541W WO 2021027172 A1 WO2021027172 A1 WO 2021027172A1
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hole transport
transport material
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the invention relates to the field of display technology, in particular to a hole transport material, a preparation method thereof, and an organic electroluminescence device.
  • OLED Organic Light-emitting Diode
  • OLED has the advantages of active light emission, high luminous efficiency, large viewing angle, fast response speed, low driving voltage, low energy consumption, lighter and thinner, and its huge application. The prospect has received widespread attention from the industry.
  • the light-emitting guest material is very important to its performance.
  • the light-emitting guest materials used in early OLEDs were fluorescent materials. Since the ratio of singlet and triplet excitons in OLEDs is 1:3, the theoretical internal quantum efficiency (IQE) of OLEDs based on fluorescent materials can only reach 25%. , Which greatly limits its application in fluorescent electroluminescent devices; heavy metal complex phosphorescent materials due to the spin-orbit coupling of heavy atoms, so that they can simultaneously use singlet and triplet excitons to achieve 100% theoretical Quantum efficiency, however, most of the commonly used heavy metals are precious metals such as iridium and platinum, and heavy metal complex phosphorescent materials have yet to be broken through in blue light materials.
  • the hole transport layer is thicker than other film layers, and its energy level and hole mobility have always been contradictory. Therefore, holes with matching energy levels and high mobility have been developed. The transfer of materials is imminent.
  • the present invention provides a hole transport material, a preparation method thereof, and an organic electroluminescent device, so as to solve the mismatch between the HOMO energy level of the hole transport material and the LUMO energy level in the existing OLED light emitting device, and the hole transport material
  • the migration rate is not high, which affects the luminous efficiency of the OLED device.
  • the present invention provides a hole transport material, the general structure of which is shown in the following formula (A):
  • the R group is a carbazole group and its derivative group, a diphenylamine group and its derivative group, a phenoxazine group and its derivative group, and an acridine group and its derivative group. Any one of the group.
  • the R group is one of the following structural formulas:
  • the present invention also provides a method for preparing the hole transport material, the structure general formula of the hole transport material is shown in formula (A):
  • the R group is a carbazole group and its derivative group, a diphenylamine group and its derivative group, a phenoxazine group and its derivative group, and an acridine group and its derivative group
  • the method for preparing the hole transport material includes the following steps:
  • the second reactant is any of carbazole and its derivatives, diphenylamine and its derivatives, phenoxazine and its derivatives, and acridine and its derivatives One kind.
  • the second reactant is any one of carbazole, phenoxazine, and 9,9'-dimethylacridine.
  • the structural formula of the first reactant is as shown in formula (B):
  • the preparation method of the first reactant includes:
  • the reaction temperature is 120 degrees Celsius
  • the reaction time is 24 hours.
  • the S30 includes:
  • the present invention also provides an organic electroluminescent device, comprising a hole transport material, and the general structure of the hole transport material is shown in the following formula (A):
  • the R group is a carbazole group and its derivative group, a diphenylamine group and its derivative group, a phenoxazine group and its derivative group, and an acridine group and its derivative group. Any one of the group.
  • the R group is one of the following structural formulas:
  • the beneficial effects of the present invention are: by using the diacridine structure as the core and collocation of different functional groups, a hole transport material with a suitable energy level and a high migration rate is designed and synthesized, and the organic electro-induced electrophoresis based on the hole transport material
  • the light-emitting device has high luminous efficiency.
  • Figure 1 is a flow chart of the steps of a method for preparing a hole transport material according to an embodiment of the present invention
  • Fig. 3 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present invention.
  • the present invention is directed to the technical problem of the existing OLED light emitting device. Due to the mismatch between the HOMO energy level and the LUMO energy level of the hole transport material, the migration rate of the hole transport material is not high, thereby affecting the luminous efficiency of the OLED device. This embodiment Can solve this defect.
  • the embodiment of the present invention provides a hole transport material, the general structure of which is shown in the following formula (A):
  • the R group is a carbazole group and its derivative group, a diphenylamine group and its derivative group, a phenoxazine group and its derivative group, and an acridine group and its derivative group Any of them.
  • carbazole group and its derivative group can be any one of the following structural formulas, but not limited to the following structural formulas:
  • the diphenylamine group and its derivative group can be any one of the following structural formulas, but not limited to the following structural formulas:
  • the phenoxazine group and its derivative group can be any one of the following structural formulas, but not limited to the following structural formulas:
  • the acridine group and its derivative group can be any one of the following structural formulas, but not limited to the following structural formulas:
  • this embodiment provides a method for preparing the above hole transport material, including the following steps:
  • the general structural formula (B) of the first reactant is shown in:
  • the structural formula of the second reactant corresponds to the R group, and can be any one of carbazole and its derivatives, diphenylamine and its derivatives, phenoxazine and its derivatives, and acridine and its derivativeskind.
  • the hole transport material has a diacridine structure as the core. Because diacridine has a strong electron-donating ability, coupled with other electron-donating groups, the synthesized material has a higher migration rate, and the present invention Example The structure of the synthesized hole transport material was confirmed by mass spectrometry. The present invention will be described in detail below through the preparation method of the hole transport material.
  • the reaction solution was poured into 200 mL ice water, extracted three times with dichloromethane, and the organic phases were combined and spun into silica gel. Separation and purification by column chromatography (volume ratio of dichloromethane and n-hexane is 1:5) to obtain target compound 1.
  • the target compound 1 is 2.2 g of white powder with a yield of 64%. Mass spectrometry analysis of the white powder yielded MS (EI) m/z: [M] + : 691.39, and the theoretical relative molecular mass of the target compound 1 was 691.40.
  • the HOMO electrochemical energy level of the target compound 1 is -5.58 eV, and the LUMO electrochemical energy level is -2.60 eV.
  • the preparation method of the first reactant includes:
  • the synthesis process of the first reactant is as follows:
  • the second intermediate (2.52 g, 5 mmol) was added to a 250 mL two-necked flask, 100 mL of acetone previously dewatered and deoxygenated was injected under an argon atmosphere, and reacted at 60° C. for 24 hours. Pour the reaction solution into 200 mL ice water, extract with dichloromethane three times, combine the organic phases, spin into silica gel, and separate and purify by column chromatography (dichloromethane: n-hexane, v: v, 1:1) to obtain 1.70 g of white powder , The yield is 76%. MS(EI) m/z: [M] + : 449.10, the theoretical relative molecular mass of the third intermediate is 449.17.
  • this embodiment also provides an organic electroluminescent device, which includes an anode 10, a hole injection layer 20, a hole transport layer 30, and an electron blocking layer 40 stacked in sequence. , The light-emitting layer 50, the hole blocking layer 60, the electron transport layer 7, the electron injection layer 80, and the cathode 90.
  • the organic electroluminescent device further includes a light outcoupling layer disposed on the cathode 90.
  • the material of the hole transport layer is prepared by the above method, and the material of the hole transport layer is target compound 1.
  • the maximum current efficiency of the hole transport layer in this embodiment is 38.9 cd/A, and the chromatogram coordinates are (0.685, 0.290) and the maximum external quantum efficiency is 36.7%.
  • the reaction solution was poured into 200 mL ice water, extracted with dichloromethane three times, the organic phases were combined, spinned to silica gel, and separated and purified by column chromatography (dichloromethane: n-hexane, v: v, 1:5) to obtain
  • the target compound 2 is 2.6 g of white powder, and the yield is 74%.
  • the HUMO electrochemical energy level of the target compound 2 is -5.61 eV, and the LUMO electrochemical energy level is -2.61 eV.
  • this embodiment also provides an organic electroluminescent device, which includes an anode 10, a hole injection layer 20, a hole transport layer 30, and an electron blocking layer 40 stacked in sequence. , The light-emitting layer 50, the hole blocking layer 60, the electron transport layer 7, the electron injection layer 80, and the cathode 90.
  • the organic electroluminescent device further includes a light outcoupling layer disposed on the cathode 90.
  • the material of the hole transport layer is prepared by the above method, and the material of the hole transport layer is the target compound 2.
  • the maximum current efficiency of the hole transport layer in this embodiment is 35.2 cd/A, and the chromatogram coordinates are (0.685, 0.290) and the maximum external quantum efficiency is 32.3%.
  • the HUMO electrochemical energy level of the target compound 3 is -5.66 eV, and the LUMO electrochemical energy level is -2.61 eV.
  • this embodiment also provides an organic electroluminescent device, which includes an anode 10, a hole injection layer 20, a hole transport layer 30, and an electron blocking layer 40 stacked in sequence. , The light-emitting layer 50, the hole blocking layer 60, the electron transport layer 7, the electron injection layer 80, and the cathode 90.
  • the organic electroluminescent device further includes a light outcoupling layer disposed on the cathode 90.
  • the material of the hole transport layer is prepared by the above method, and the material of the hole transport layer is target compound 3.
  • the maximum current efficiency of the hole transport layer in this embodiment is 36.8 cd/A, and the chromatogram coordinates are (0.685, 0.290) and the maximum external quantum efficiency is 33.5%.
  • the hole transport material with suitable energy level and high migration rate is designed and synthesized by using the diacridine structure as the nucleus and matching different functional groups, and the organic electroluminescent device based on the hole transport material has better performance. High luminous efficiency.

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Abstract

一种空穴传输材料，其结构通式为 (A),R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种。通过以二并吖啶结构为核，设计合成了具有合适能级且迁移速率高的空穴传输材料，且基于该空穴传输材料的有机电致发光器件具有较高的发光效率。

Description

空穴传输材料及其制备方法、有机电致发光器件
本申请要求于2019年08月13日提交中国专利局、申请号为201910744472.0、发明名称为“空穴传输材料及其制备方法、有机电致发光器件”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及显示技术领域，尤其涉及一种空穴传输材料及其制备方法、有机电致发光器件。
背景技术
有机电致发光二极管(Organic Light-emitting Diode，OLED)以其主动发光、发光效率高、可视角度大、响应速度快、驱动电压低，能耗小，更轻薄化等优势以及其巨大的应用前景，受到业界广泛关注。在OLED发光材料中，发光客体材料对其性能至关重要。
早期的OLED采用的发光客体材料为荧光材料，由于在OLED中单重态和三重态的激子比例为1:3，因此基于荧光材料的OLED的理论内量子效率(IQE)只能达到25％，极大地限制了其在荧光电致发光器件的应用；重金属配合物磷光材料由于重原子的自旋轨道耦合作用，使之能够同时利用单重态和三重态激子而实现100％的理论内量子效率，然而，通常使用的重金属大部分为铱、铂等贵重金属，并且重金属配合物磷光发光材料在蓝光材料方面尚有待突破。
对于目前使用的顶发射OLED器件中，空穴传输层较其他膜层的厚度更厚，其能级以及空穴迁移率一直存在相互矛盾的关系，因此开发匹配能级以及高迁移率的空穴传输材料迫在眉睫。
技术问题
本发明提供一种空穴传输材料及其制备方法、有机电致发光器件，以解决现有的OLED发光器件中，空穴传输材料的HOMO能级和LUMO能级不匹配，空穴传输材料的迁移速率不高，进而影响OLED器件的发光效率的技术问题。
技术解决方案
为解决上述问题，本发明提供的技术方案如下：
本发明提供一种空穴传输材料，结构通式如下式(A)式所示：
Figure PCTCN2019119541-appb-000001
其中，R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种。
在本发明的至少一种实施例中，所述R基团为下列结构式中的一种：
Figure PCTCN2019119541-appb-000002
Figure PCTCN2019119541-appb-000003
在本发明还提供一种空穴传输材料的制备方法，所述空穴传输材料的结构通式如式(A)所示：
Figure PCTCN2019119541-appb-000004
其中R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种，所述空穴传输材料的制备方法包括以下步骤：
S10，将第一反应物、第二反应物以及醋酸钯、三叔丁基膦四氟硼酸盐混合，得到混合液；
S20，将所述混合液置于手套箱中，并向所述混合液中加入叔丁醇钠、甲苯，反应并冷却至室温得到反应液；
S30，对所述反应液进行萃取、合并有机相，对所述有机相进行分离纯化，得到所述空穴传输材料。
在本发明的至少一种实施例中，所述第二反应物为咔唑及其衍生物、二苯胺及其衍生物、吩恶嗪及其衍生物、以及吖啶及其衍生物中的任意一种。
在本发明的至少一种实施例中，所述第二反应物为咔唑、吩恶嗪以及9,9’-二甲基吖啶中的任意一种。
在本发明的至少一种实施例中，所述第一反应物的结构式如式(B)所示：
Figure PCTCN2019119541-appb-000005
在本发明的至少一种实施例中，所述第一反应物的制备方法包括：
S101，将4,4'-二溴-4'-叔丁基三苯胺与氯乙酰氯反应得到第一中间体，所述第一中间体的结构式如式(C)所示：
Figure PCTCN2019119541-appb-000006
S102，将所述第一中间体与氰化亚铜、氯化亚铁反应，得到第二中间体，所述第二中间体的结构式如式(D)所示：
Figure PCTCN2019119541-appb-000007
S103，将所述第二中间体与丙酮反应得到第三中间体，所述第三中间体的 结构式如式(E)所示：
Figure PCTCN2019119541-appb-000008
S104，将所述第三中间体与4-溴-2,3,5,6-四甲基苯胺反应得到所述第一反应物。
在本发明的至少一种实施例中，在所述S20中，反应温度为120摄氏度，反应时间为24小时。
在本发明的至少一种实施例中，所述S30包括：
将所述反应液倒入冰水后，利用二氯甲烷萃取数次后，合并有机相；
将所述有机相旋成硅胶后，利用柱层析法进行分离纯化得到所述空穴传输材料。
本发明还提供一种有机电致发光器件，包括空穴传输材料，所述空穴传输材料的结构通式如下式(A)所示：
Figure PCTCN2019119541-appb-000009
其中，R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种。
在本发明的至少一种实施例中，所述R基团为下列结构式中的一种：
Figure PCTCN2019119541-appb-000010
有益效果
本发明的有益效果为：通过以二并吖啶结构为核和搭配不同的官能团，设计合成了具有合适能级且迁移速率高的空穴传输材料，且基于该空穴传输材料的有机电致发光器件具有较高的发光效率。
附图说明
为了更清楚地说明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单介绍，显而易见地，下面描述中的附图仅仅是发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例的空穴传输材料的制备方法的步骤流程图；
图2为本发明实施例的第一反应物的制备方法的步骤流程图；
图3为本发明实施例的有机电致发光器件的结构示意图。
本发明的实施方式
以下各实施例的说明是参考附加的图示，用以例示本发明可用以实施的特定实施例。本发明所提到的方向用语，例如[上]、[下]、[前]、[后]、[左]、[右]、[内]、[外]、[侧面]等，仅是参考附加图式的方向。因此，使用的方向用语是用以说明及理解本发明，而非用以限制本发明。在图中，结构相似的单元是用以相同标号表示。
本发明针对现有的OLED发光器件，由于空穴传输材料的HOMO能级和LUMO能级不匹配，空穴传输材料的迁移速率不高，进而影响OLED器件的发光效率的技术问题，本实施例能够解决该缺陷。
本发明实施例提供一种空穴传输材料，其结构通式如下式(A)所示：
Figure PCTCN2019119541-appb-000011
其中R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种。
具体地，所述咔唑基团及其衍生物基团可以为下列结构式中的任意一种，但不限于下列结构式：
Figure PCTCN2019119541-appb-000012
所述二苯胺基团及其衍生物基团可以为下列结构式中的任意一种，但不限于下列结构式：
Figure PCTCN2019119541-appb-000013
所述吩恶嗪基团及其衍生物基团可以为下列结构式中的任意一种，但不限于下列结构式：
Figure PCTCN2019119541-appb-000014
所述吖啶基团及其衍生物基团可以为下列结构式中的任意一种，但不限于下列结构式：
Figure PCTCN2019119541-appb-000015
如图1所示，本实施例提供一种上述空穴传输材料的制备方法，包括以下步骤：
S10，将第一反应物、第二反应物以及醋酸钯、三叔丁基膦四氟硼酸盐混合，得到混合液；
S20，将所述混合液置于手套箱中，并向所述混合液中加入叔丁醇钠、甲苯，反应并冷却至室温得到反应液；
S30，对所述反应液进行萃取、合并有机相，对所述有机相进行分离纯化，得到所述空穴传输材料。
所述第一反应物的结构通式式(B)所示：
Figure PCTCN2019119541-appb-000016
所述第二反应物的结构式与R基团相对应，可为咔唑及其衍生物、二苯胺及其衍生物、吩恶嗪及其衍生物、以及吖啶及其衍生物中的任意一种。
所述空穴传输材料以二并吖啶结构为核，由于二并吖啶具有很强的给电子能力，再配上其他给电子基团，合成的材料具有较高的迁移速率，并且本发明实施例通过质谱分析对合成的空穴传输材料进行结构确认。下面通过所述空穴传输材料的制备方法对本发明进行详细介绍。
实施例一
向250mL二口瓶中加入第一反应物(3.02g，5mmol)、咔唑(1.00g，6mmol)、醋酸钯(45mg，0.2mmol)、三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，得到混合液，然后将所述混合液置于手套箱中，再向混合液中加入叔丁醇钠(NaOt-Bu，0.58g，6mmol)，之后在氩气氛围下打入100mL事先除水除氧的甲苯，在120℃反应24小时，并冷却至室温得到反应液，将所述反应液倒入200mL冰水中，利用二氯甲烷萃取三次后合并有机相，并旋成硅胶，通过柱层析(二氯甲烷与正己烷的体积比为1:5)分离纯化，得到目标化合物1，该目标化合物1为2.2g的白色粉末，产率为64％。对该白色粉末进行质谱图分析得到MS(EI)m/z:[M] +:691.39，所述目标化合物1的理论相对分子质量为691.40。
其中，所述空穴传输材料的合成路线如下式(1)所示：
Figure PCTCN2019119541-appb-000017
所述目标化合物1的HOMO电化学能级为-5.58eV，LUMO电化学能级为-2.60eV。
如图2所示，所述第一反应物的制备方法包括：
S101，将4,4'-二溴-4'-叔丁基三苯胺与氯乙酰氯反应得到第一中间体，所述第一中间体的结构式如式(C)所示：
Figure PCTCN2019119541-appb-000018
S102，将所述第一中间体与氰化亚铜、氯化亚铁反应，得到第二中间体，所述第二中间体的结构式如式(D)所示：
Figure PCTCN2019119541-appb-000019
S103，将所述第二中间体与丙酮反应得到第三中间体，所述第三中间体的结构式如式(E)所示：
Figure PCTCN2019119541-appb-000020
S104，将所述第三中间体与4-溴-2,3,5,6-四甲基苯胺反应得到所述第一反 应物。
所述第一反应物的合成过程如下所示：
Figure PCTCN2019119541-appb-000021
具体地，在所述S101中，向250mL二口瓶中加入4,4'-二溴-4'-叔丁基三苯胺(4.57g，10mmol)，氯乙酰氯(16.7g，100mmol)，在氩气氛围下打入100mL事先除水除氧的甲苯，在室温下反应24小时。将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，2:1)分离纯化，得到白色粉末3.37g，产率51％。对该白色粉末进行质谱图分析得到MS(EI)m/z:[M] +:660.73，第一中间体的理论相对分子质量为660.77。
在所述S102中，向250mL二口瓶中加入所述第一中间体(3.3g，5mmol)，氰化亚铜(0.54g，60mmol)，在氩气氛围下打入100mL事先除水除氧的甲苯，在100℃下反应24小时，然后加入二氯化铁(0.75g,60mmol)。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，2:1)分离纯化，得白色粉末2.01g，产率83％。对该白色粉末进行质谱图分析，MS(EI)m/z:[M] +:504.88，第二中间体的理论相对分子质量为504.95。
在所述S103中，向250mL二口瓶中加入所述第二中间体(2.52g，5mmol)，在氩气氛围下打入100mL事先除水除氧的丙酮，在60℃下反应24小时。将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:1)分离纯化，得白色粉末1.70g，产率76％。 MS(EI)m/z:[M] +:449.10，第三中间体的理论相对分子质量为449.17。
在所述S104中，向250mL二口瓶中加入所述第三中间体(2.25g，5mmol)，4-溴-2,3,5,6-四甲基苯胺(1.39g,6mmol)在氩气氛围下打入100mL事先除水除氧的丙酮，在60℃下反应24小时。将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:1)分离纯化，得白色粉末2.41g，产率80％。MS(EI)m/z:[M] +:604.13，第一反应物的理论相对分子质量为604.25。
如图3所示，本实施例还提供一种有机电致发光器件，所述有机电致发光器件包括依次层叠设置的阳极10、空穴注入层20、空穴传输层30、电子阻挡层40、发光层50、空穴阻挡层60、电子传输层7、电子注入层80、以及阴极90，所述有机电致发光器件还包括设置于所述阴极90上的光耦合输出层。其中，所述空穴传输层的材料采用上述方法制备，所述空穴传输层材料为目标化合物1。
本实施例中的空穴传输层的最高电流效率为38.9cd/A，色谱图坐标为(0.685,0.290)最大外量子效率为36.7％。
实施例二
向250mL二口瓶中加入第一反应物(3.02g，5mmol)，吩恶嗪(1.10g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入100mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:5)分离纯化，得到目标化合物2，该目标化合物2为2.6g的白色粉末，产率74％。MS(EI)m/z:[M] +:707.32，所述目标化合物2的理论相对分子质量为707.37。
其中，所述空穴传输材料的合成路线如下式(2)所示
Figure PCTCN2019119541-appb-000022
所述目标化合物2的HUMO电化学能级为-5.61eV，LUMO电化学能级为-2.61eV。
如图3所示，本实施例还提供一种有机电致发光器件，所述有机电致发光器件包括依次层叠设置的阳极10、空穴注入层20、空穴传输层30、电子阻挡层40、发光层50、空穴阻挡层60、电子传输层7、电子注入层80、以及阴极90，所述有机电致发光器件还包括设置于所述阴极90上的光耦合输出层。其中，所述空穴传输层的材料采用上述方法制备，所述空穴传输层材料为目标化合物2。
本实施例中的空穴传输层的最高电流效率为35.2cd/A，色谱图坐标为(0.685,0.290)最大外量子效率为32.3％。
实施例三
向250mL二口瓶中加入第一反应物(3.02g，5mmol)，9,9’-二甲基吖啶(1.26g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入100mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:5)分离纯化，得到目标化合物3，所述目标化合物3为2.4g的白色粉末，产率65％。MS(EI)m/z:[M] +:733.41，所述目标化合物3的理论相对分子质量为733.44。
其中，所述空穴传输材料的合成路线如下式(3)所示：
Figure PCTCN2019119541-appb-000023
所述目标化合物3的HUMO电化学能级为-5.66eV，LUMO电化学能级为-2.61eV。
如图3所示，本实施例还提供一种有机电致发光器件，所述有机电致发光器件包括依次层叠设置的阳极10、空穴注入层20、空穴传输层30、电子阻挡层40、发光层50、空穴阻挡层60、电子传输层7、电子注入层80、以及阴极 90，所述有机电致发光器件还包括设置于所述阴极90上的光耦合输出层。其中，所述空穴传输层的材料采用上述方法制备，所述空穴传输层材料为目标化合物3。
本实施例中的空穴传输层的最高电流效率为36.8cd/A，色谱图坐标为(0.685,0.290)最大外量子效率为33.5％。
有益效果：通过以二并吖啶结构为核和搭配不同的官能团，设计合成了具有合适能级且迁移速率高的空穴传输材料，且基于该空穴传输材料的有机电致发光器件具有较高的发光效率。
综上所述，虽然本发明已以优选实施例揭露如上，但上述优选实施例并非用以限制本发明，本领域的普通技术人员，在不脱离本发明的精神和范围内，均可作各种更动与润饰，因此本发明的保护范围以权利要求界定的范围为准。

Claims (11)

  1. 一种空穴传输材料，其中，结构通式如下式(A)所示：
    Figure PCTCN2019119541-appb-100001
    其中，R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种。
  2. 根据权利要求1所述的空穴传输材料，其中，所述R基团为下列结构式中的一种：
    Figure PCTCN2019119541-appb-100002
    Figure PCTCN2019119541-appb-100003
  3. 一种空穴传输材料的制备方法，其中，所述空穴传输材料的结构通式如式(A)所示：
    Figure PCTCN2019119541-appb-100004
    其中R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种，所述空穴传输材料的制备方法包括以下步骤：
    S10，将第一反应物、第二反应物以及醋酸钯、三叔丁基膦四氟硼酸盐混合，得到混合液；
    S20，将所述混合液置于手套箱中，并向所述混合液中加入叔丁醇钠、甲苯，反应并冷却至室温得到反应液；
    S30，对所述反应液进行萃取、合并有机相，对所述有机相进行分离纯化，得到所述空穴传输材料。
  4. 根据权利要求3所述的制备方法，其中，所述第二反应物为咔唑及其衍生物、二苯胺及其衍生物、吩恶嗪及其衍生物、以及吖啶及其衍生物中的任 意一种。
  5. 根据权利要求4所述的制备方法，其中，所述第二反应物为咔唑、吩恶嗪以及9,9’-二甲基吖啶中的任意一种。
  6. 根据权利要求4所述的制备方法，其中，所述第一反应物的结构式如式(B)所示：
    Figure PCTCN2019119541-appb-100005
  7. 根据权利要求6所述的制备方法，其中，所述第一反应物的制备方法包括：
    S101，将4,4'-二溴-4'-叔丁基三苯胺与氯乙酰氯反应得到第一中间体，所述第一中间体的结构式如式(C)所示：
    Figure PCTCN2019119541-appb-100006
    S102，将所述第一中间体与氰化亚铜、氯化亚铁反应，得到第二中间体，所述第二中间体的结构式如式(D)所示：
    Figure PCTCN2019119541-appb-100007
    S103，将所述第二中间体与丙酮反应得到第三中间体，所述第三中间体的 结构式如式(E)所示：
    Figure PCTCN2019119541-appb-100008
    S104，将所述第三中间体与4-溴-2,3,5,6-四甲基苯胺反应得到所述第一反应物。
  8. 根据权利要求3所述的制备方法，其中，在所述S20中，反应温度为120摄氏度，反应时间为24小时。
  9. 根据权利要求3所述的制备方法，其中，所述S30包括：
    将所述反应液倒入冰水后，利用二氯甲烷萃取数次后，合并有机相；
    将所述有机相旋成硅胶后，利用柱层析法进行分离纯化得到所述空穴传输材料。
  10. 一种有机电致发光器件，包括空穴传输材料，其中，所述空穴传输材料的结构通式如下式(A)所示：
    Figure PCTCN2019119541-appb-100009
    其中，R基团为咔唑基团及其衍生物基团、二苯胺基团及其衍生物基团、吩恶嗪基团及其衍生物基团、以及吖啶基团及其衍生物基团中的任意一种。
  11. 根据权利要求10所述的有机电致发光器件，其中，所述R基团为下列结构式中的一种：
    Figure PCTCN2019119541-appb-100010
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