WO2016058504A1 - 芳香族胺衍生物及其有机电致发光器件 - Google Patents

芳香族胺衍生物及其有机电致发光器件 Download PDF

Info

Publication number
WO2016058504A1
WO2016058504A1 PCT/CN2015/091702 CN2015091702W WO2016058504A1 WO 2016058504 A1 WO2016058504 A1 WO 2016058504A1 CN 2015091702 W CN2015091702 W CN 2015091702W WO 2016058504 A1 WO2016058504 A1 WO 2016058504A1
Authority
WO
WIPO (PCT)
Prior art keywords
mmol
compound
tert
same
added
Prior art date
Application number
PCT/CN2015/091702
Other languages
English (en)
French (fr)
Inventor
黄达
孙艳雪
李正
谭玉东
Original Assignee
江苏和成新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏和成新材料有限公司 filed Critical 江苏和成新材料有限公司
Publication of WO2016058504A1 publication Critical patent/WO2016058504A1/zh

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54Compounds 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54Compounds 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
    • C07C211/56Compounds 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 the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/30Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/49Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the invention belongs to the technical field of organic electroluminescent materials, and relates to an aromatic amine compound and an organic electroluminescent device using the same.
  • An organic electroluminescence device (organic EL device) is a self-luminous device which utilizes the principle that a hole injected from an anode and an electron injected from a cathode are combined to cause a substance to emit light by applying an electric field.
  • NPB N, N'-di ( 1-Naphthyl)-N,N'-diphenyl-4,4'-benzidine
  • NPB N, N'-di ( 1-Naphthyl)-N,N'-diphenyl-4,4'-benzidine
  • JP2006273785A and WO2006006505A1 provide an aromatic amine compound in which an amine-substituted benzene ring is ortho-linked;
  • KR1020090093024A discloses a class of aromatic amine structures in which a linking group contains five benzene rings, which is required for synthesis.
  • An object of the present invention is to provide an aromatic amine compound which has a high glass transition temperature, is difficult to crystallize, and is easily synthesized.
  • the aromatic amine derivative provided by the invention has a symmetrical structure and is easy to synthesize; the high molecular weight makes the compound have a high glass transition temperature and good stability, and can well overcome the problem that the common symmetrical compound is easily crystallized.
  • Another object of the present invention is to provide an application of such an aromatic amine compound in an organic EL device.
  • the present invention provides a biphenyl-based aromatic amine compound having a structure of the formula I; the present invention limits the number of benzene rings in a biphenyl-based aromatic amine compound, and a fluorine atom or a cyano group.
  • an electron withdrawing group such as an alkyl group or an electron-donating group makes it easy to obtain a stable compound material in accordance with an organic EL device.
  • Rx, Ry 1 , Ry 2 , Rz 1 and Rz 2 are the same or different and each independently represents -H, -F, -CN, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group;
  • a, b, c, d and e are the same or different, each independently represents 0, 1, 2, 3 or 4, and when a>1, Ry 1 may be a different substituent, and when b>1, Ry 2 may be Different substituents; when c>1, Rz 1 may be different substituents; when d>1, Rz 2 may be different substituents; when e>1, Rx is the same substituent.
  • the Rx, Ry 1 , Ry 2 , Rz 1 and Rz 2 are the same or different and each independently represents -H, -F, -CN, methyl, ethyl, n-propyl. , isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the Rx, Ry 1 , Ry 2 , Rz 1 and Rz 2 are the same or different and each independently represents -H, -F, -CN, methyl, ethyl, n-propyl. , isopropyl, n-butyl or tert-butyl.
  • the Rx, Ry 1 , Ry 2 , Rz 1 and Rz 2 are the same or different and each independently represents -H, -CN, methyl, n-propyl, isopropyl, and Butyl or tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the compound of formula I has a relative molecular weight of no more than 1500, preferably in the range of from 850 to 1450.
  • the compound of Formula I is selected from the group consisting of the compounds of Formulas I-1 to I-14:
  • Ry 1 , Ry 2 , Rz 1 and Rz 2 are the same or different and each independently represents -H, -F, -CN, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group;
  • a, b, c and d are the same or different, each independently represents 0, 1, 2, 3 or 4, and when a>1, Ry 1 may be the same or different substituents, and when b>1, Ry 2 may Are the same or different substituents; when c>1, Rz 1 may be the same or different substituents; when d>1, Rz 2 may be the same or different substituents.
  • aromatic amine compound represented by the general formula I of the present invention is shown below, but are not limited to these exemplified compounds.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 and L are each of the formula III, the formula IV, the formula V, the formula VI and the formula VII:
  • Rx, Ry 1 , Ry 2 , Rz 1 and Rz 2 are the same or different and each independently represents -H, -F, -CN, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group;
  • a, b, c, d and e are the same or different, each independently represents 0, 1, 2, 3 or 4, and when a>1, Ry 1 may be the same or different substituents, and when b>1, Ry 2 may be the same or different substituents; when c>1, Rz 1 may be the same or different substituent; when d>1, Rz 2 may be the same or different substituent; when e>1, it may be the same Or different substituents,
  • the compound of Formula I is preferably one or more of the following:
  • the present invention also provides a method of synthesizing the aromatic amine derivative of the formula I, namely the Buchwald-Hartwig coupling method known in the art:
  • the aromatic amine represented by the formula (a) and the formula (b) and the dihalogen represented by the formula (c) are sequentially added to a mixed solvent of toluene-ethanol and water, and 0.05 mol% of a palladium acetate catalyst and a special amount are charged.
  • the tert-butylphosphine is heated and stirred for 2-8 hours, and then worked up to obtain the corresponding product of the formula (I).
  • the halogen of the dihalogen is independently selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • the present invention also provides an organic electroluminescent device in which one or more organic thin film layers are sandwiched between a cathode and an anode of the organic electroluminescent device, at least one of the organic thin film layers A compound of the formula I according to the invention, alone or as a component of a mixture.
  • the compound of Formula I is used as a hole transporting material or a hole injecting material in an organic electroluminescent device.
  • the compound of Formula I is used as the host material in an organic electroluminescent device.
  • the compound of formula I acts as a blue light material in an organic electroluminescent device.
  • a typical structure of an organic EL device is an anode/hole injection layer/hole transport layer/organic light-emitting layer/electron transport layer/electron injection layer/cathode.
  • the anode layer may be made of an inorganic material, generally a metal or a metal oxide having a high work function, and indium tin oxide (hereinafter referred to as ITO) is preferred in the present invention.
  • ITO indium tin oxide
  • the hole injecting material is generally made of polythiophene/sodium polyvinylbenzenesulfonate (hereinafter referred to as PEDOT:PSS), copper phthalocyanine (CuPc), and 4,4′,4′′-tris(N-3-methylphenyl- N-phenylamino)triphenylamine (m-MTDATA), preferably polythiophene/sodium polyvinylbenzenesulfonate (PEDOT:PSS).
  • PEDOT:PSS polythiophene/sodium polyvinylbenzenesulfonate
  • CuPc copper phthalocyanine
  • m-MTDATA 4,4′,4′′-tris(N-3-methylphenyl- N-phenylamino)triphenylamine
  • PEDOT:PSS polythiophene/sodium polyvinylbenzenesulfonate
  • the hole transport layer is generally a triarylamine-based material such as N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1-biphenyl-4,4-diamine (NPB).
  • NPB N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1-biphenyl-4,4-diamine
  • the luminescent layer may be a single luminescent material, or a combination of host material and dopant material, common tris(8-hydroxyquinoline) aluminum, 9,10-two (2 -naphthyl) anthracene.
  • the electron transport layer is generally a metal organic complex such as tris(8-hydroxyquinoline)aluminum or a benzimidazole such as 1,3,5-tris(1-phenyl-1H-benzimidazole-2 -Based benzene (TBPI) or the like;
  • the electron injecting material is generally an inorganic fluoride such as lithium fluoride (LiF) or cesium fluoride (CsF), and lithium fluoride (LiF) is preferred in the present invention.
  • the cathode layer is generally made of a metal having a lower work function such as lithium, magnesium, calcium, strontium, aluminum or indium or an alloy of any of them with copper, gold or silver.
  • the device preparation method of the present invention is as follows:
  • a hole injecting layer was prepared. Preparing a hole injecting layer of the device by spin coating or evaporation;
  • a hole transport layer was prepared. Preparing a hole transport layer of the device by spin coating or evaporation;
  • a luminescent layer was prepared. Preparing a light-emitting layer of the device by spin coating or evaporation;
  • a metal cathode is prepared by evaporation or sputtering.
  • the aromatic amine compound of the terphenyl-4,4'-diyl derivative has a steric hindrance due to steric hindrance, and the aroma of the present invention is provided.
  • the structure of the amine compound is symmetrical, easy to synthesize, and the molecular weight is high, so that the compound has high glass transition temperature and good stability, and can well overcome the problem that the common symmetrical compound is easy to crystallize, making the material easier to form a film to improve the yield of the manufactured device, and prolonging the organic
  • the lifetime of the EL device In particular, the combination with the blue luminescent material is more effective; in addition, the introduction of an alkyl chain into the molecular structure can improve the solubility of the compound, and introduction of an electron withdrawing group such as a cyano group and a fluorine atom can increase the EA value and lower the LUMO level, thereby lowering the compound.
  • the energy gap that is, the aromatic amine compound of the present invention can be
  • Figure 1 is a graph showing the lumen efficiency and brightness of Device 1, Device 2, Device 3, Device 4, and Comparative Compound NPB;
  • Figure 2 is a plot of current efficiency and brightness for Device 1, Device 2, Device 3, Device 4, and Comparative Compound NPB.
  • Biphenyl-N-2-butylbenzidine 1 mmol 2-isopropylbiphenyl-N-2-isopropylbenzidine, 0.1% mmol palladium acetate, 0.4 mmol tert-butylphosphine, 30 mmol uncle butoxide, in a reaction at 100 °C 4 hours, cooled to room temperature 50ml of water was added, the organic layer was extracted, and methanol was added to the organic layer to precipitate a solid, and recrystallized from toluene to give a white powder, is the compound H75.
  • the organic EL device can be prepared as follows:
  • the glass plate coated with the transparent conductive layer of ITO is sonicated in a cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, and baked in a clean environment to completely remove water, using ultraviolet light.
  • the washing machine is irradiated for 10 minutes and bombards the surface with a low energy cation beam;
  • a hole injecting layer was prepared.
  • the PEDOT:PSS aqueous solution was spin-coated at a certain rotation speed, and then annealed at 120 ° C for 15 minutes to form a hole injection layer;
  • a hole transport layer was prepared. On the hole injection layer, a certain thickness of the compound containing the formula (H1) is evaporated as a hole transport layer, the evaporation rate is 0.1 nm / s;
  • a luminescent layer was prepared. On the hole transport layer, a certain thickness of the light-emitting layer containing ADN and AlQ3 is evaporated, the evaporation rate is 0.1 nm / s;
  • Device Example 2 was prepared in the same manner as in Device Example 1, except that Formula H2 was replaced by Formula H1 in Device Example 1.
  • the device example 3 was prepared in the same manner as in the device example 1 except that the formula H29 was replaced with the formula H1 in the device example 1.
  • the device example 4 was prepared in the same manner as in the device example 1 except that the formula H79 was replaced with the formula H1 in the device example 1.
  • the device example 5 was prepared in the same manner as in the device example 1 except that the formula H62 was replaced with the formula H1 in the device example 1.
  • the device is prepared according to the device embodiment 1 in other manners.
  • the comparative example was prepared in the same manner as in the device example 1 except that the NPB was replaced with the formula H1 in the device example 1.
  • HTL life Device Embodiment 1 H1 10h Device Embodiment 2 H2 10h Device Embodiment 3 H29 9h Device Embodiment 4 H79 7h Device Example 5 H62 7h Device Example 6 H104 8h Comparative example NPB 4h
  • the glass transition temperature of NPB is not high enough, and it is easy to crystallize at the applied voltage, resulting in a decrease in lifetime.
  • the lifetime of each device embodiment is higher than that of the comparative NPB embodiment, indicating that the material of the present invention is superior to NPB in stability over NPB and can be used as an alternative hole transporting material.
  • the aromatic amine compound of the present invention has the advantages of being difficult to crystallize, having good film forming property, high thermal stability, and easy synthesis, and can prepare a long-life organic EL device, which is extremely industrially feasible.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Luminescent Compositions (AREA)

Abstract

一种如通式I所示的芳香胺衍生物及其合成方法和应用,以及一种有机电致发光器件。该化合物结构对称,容易合成,分子量较高,玻璃化温度高,稳定性好,能够克服容易结晶的缺陷,可以作为有机电致发光元件中的空穴输送材料或发光材料。该有机电致发光器件在阴极和阳极间夹有至少包含发光层的由一层或多层组成的有机薄膜,该有机薄膜的至少一层作为单独组分或混合物组分含有所述芳香胺化合物。

Description

芳香族胺衍生物及其有机电致发光器件 技术领域
本发明属于有机电致发光材料技术领域,涉及一种芳香族胺化合物以及使用该类化合物的有机电致发光器件。
背景技术
有机电致发光器件(有机EL器件),是利用施加电场后从阳极注入的空穴与从阴极注入的电子复合能引起物质发光这一原理的一种自发光器件。
有机电致发光器件在高温环境下工作时,会产生发光颜色变化、发光效率降低、驱动电压上升以及器件寿命缩短等不良现象。为了解决这些问题,必须提高材料的玻璃化温度(Tg)。因为芳香族胺类化合物具有低的电离能,氮原子具有很强的给电子能力,容易发生分子间的Marcus电子转移[J.Am.Chem.Soc.,1966,88,3498],在电场的不间断给出电子过程中表机出空穴传输能力,所以常用的空穴传输材料大多数为芳香族胺类化合物,分子中包含多个芳香族基团。现有工业生产中,目前研究较为成熟的是以联苯基团作为连接基团的芳香族二胺衍生物,最为常见的是具有稠合芳环的胺衍生物如N,N’-二(1-萘基)-N,N’-二苯基-4,4’-联苯胺(简称NPB)作为空穴传输材料。然而,采用这类空穴输送材料形成薄膜以制造有机EL元件时,容易引起结晶化,堵塞蒸镀的坩埚出口,或导致有机EL元件成品率降低等问题。由于联苯基团过于刚性,在有机溶剂中溶解度较差导致不易提纯,进而很容易产生结晶。
为了解决这些问题,JP2006273785A和WO2006006505A1提供的芳香胺类化合物,其胺所连苯环采用邻位连接方式;KR1020090093024A公开了一类芳香胺结构,其中的连接基团包含五个苯环,合成需要用到特殊的硅试剂;JP2008007424A、US20070111028A1以及WO2009151039A1提供的芳香胺衍生物,连接基团和胺上的苯环均不包含取代基;WO2011131185A1提供了一类联苯类芳香胺类化合物,末端基团以菲取代基和三苯甲烷基提高玻璃化温度,以烷基封端的提高溶解度。
鉴于此,在薄膜制备工艺中通常需要采用适当的措施来降低或阻止有机材料的结晶现象。一方面是增加分子空间位阻,减少分子聚集;另一方面还可以引入取代基团破坏分子的平面共轭结构,使平面发生扭曲,破坏其结晶性,同时也提高材料的溶解性。
因此,急需一种兼具高玻璃化温度、不易结晶化、溶解性能好、易合成的空穴输送材料,提高制造有机EL器件的成品率,增长器件的使用寿命。
发明内容
本发明的目的是提供一种玻璃化温度高、不易结晶、易合成的芳香族胺化合物。本发明提供的这类芳香胺衍生物结构对称,容易合成;分子量较高使得化合物的玻璃化温度高,稳定性好,能够很好地克服常见对称化合物容易结晶的问题。
本发明的另一目的是提供这类芳香族胺化合物在有机EL器件中的应用。
为了解决上述问题,本发明提供了一种联苯类芳香胺化合物,所述化合物具有通式I的结构;本发明通过对联苯类芳香胺化合物中苯环数量的限制,以及氟原子、氰基、烷基等吸电子或供电子基团的引入,容易得到符合有机EL器件的稳定的化合物材料。
Figure PCTCN2015091702-appb-000001
其中,
x为3或4;y1为1或2;y2为1或2;z1为1或2;z2为1或2;
Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、含1-6碳原子的烷基或环烷基;
a、b、c、d和e相同或不同,各自独立的表示0、1、2、3或4,且a>1时,Ry1可以为不同取代基,b>1时,Ry2可以为不同取代基;c>1时,Rz1可以为不同取代基;d>1时,Rz2可以为不同取代基;e>1时,Rx为相同取代基,
其中,y1≥z1,y1≥z2;且当z1=z2=1时,Rx不能为氢原子,e不为0。
在本发明的一些实施方式中,所述Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、环丙基、环丁基、环戊基或环己基。
在本发明的一些实施方式中,所述Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、甲基、乙基、正丙基、异丙基、正丁基或叔丁基。
在本发明的一些实施方式中,所述Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-CN、甲基、正丙基、异丙基、正丁基或叔丁基、环丙基、环丁基、环戊基或环己基。
在本发明的一些实施方式中,通式I所述化合物的相对分子量不超过1500,优选在850-1450范围内。
在本发明的一些实施方式中,通式I的化合物选自由通式I-1至I-14所示化合物组成的组:
Figure PCTCN2015091702-appb-000002
Figure PCTCN2015091702-appb-000003
Figure PCTCN2015091702-appb-000004
Figure PCTCN2015091702-appb-000005
Figure PCTCN2015091702-appb-000006
其中,
y1为1或2;y2为1或2;z1为1或2;z2为1或2;
Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、含1-6碳原子的烷基或环烷基;
a、b、c和d相同或不同,各自独立的表示0、1、2、3或4,且a>1时,Ry1可以为相同或不同的取代基,b>1时,Ry2可以为相同或不同的取代基;c>1时,Rz1可以为相同或不同的取代基;d>1时,Rz2可以为相同或不同的取代基
其中,y1≥z1,y1≥z2
前提是,在通式I-1中,当Ry1、Ry2、Rz1和Rz2表示-H时,y1=y2=z1=z2=2;y1=y2= z2=2且z1=1;或者y1=2且y2=z1=z2=1。
以下示出本发明由通式I表示的芳香族胺化合物的具体例子,但并不限于这些例示化合物。
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-1
其中,Ar1,Ar2,Ar3,Ar4及L分别为通式III,通式IV,通式V,通式VI及通式VII:
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-2
其中,
x为3或4;y1为1或2;y2为1或2;z1为1或2;z2为1或2;
Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、含1-6碳原子的烷基或环烷基;
a、b、c、d和e相同或不同,各自独立的表示0、1、2、3或4,且a>1时,Ry1可以为相同或不同的取代基,b>1时,Ry2可以为相同或不同的取代基;c>1时,Rz1可以为相同或不同的取代基;d>1时,Rz2可以为相同或不同的取代基;e>1时,可以为相同或不同的取代基,
其中,y1≥z1,y1≥z2;且当z1=z2=1时,Rx不能为氢原子,e不为0。
在本发明的一些实施方式中,通式I的化合物优选如下化合物中的一种或多种:
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-3
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-4
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-5
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-6
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-7
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-8
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-9
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-10
本发明还提供了一种合成通式I的所述芳香族胺衍生物的合成方法,即本领域公知的Buchwald-Hartwig偶联方法:
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-11
将式(a)和式(b)所示的芳香胺与式(c)所示的二卤代物按比例依次加入到甲苯-乙醇和水的混合溶剂中,投入0.05mol%醋酸钯催化剂和特叔丁基膦,加热搅拌2-8小时,后处理即可得到相应的式(I)产品。其中二卤代物的卤素独立的选自氟、氯、溴、碘。
本发明还提供了一种有机电致发光器件,其中,在所述有机电致发光器件的阴极和阳极之间夹有一层或多层有机薄膜层,所述有机薄膜层中的至少一层中含有单独的或作为混合物成分的本发明通式I的化合物。
在本发明的一些实施方式中,通式I的化合物在有机电致发光器件中作为空穴传输材料或空穴注入材料。
在本发明的一些实施方式中,通式I的化合物在有机电致发光器件中作为主体材料。
在本发明的一些实施方式中,通式I的化合物在有机电致发光器件中作为蓝光材料。
有机EL器件的典型结构为:阳极/空穴注入层/空穴传输层/有机发光层/电子传输层/电子注入层/阴极。根据目标和应用的不同,可以简化或复杂化某些功能层。
阳极层可以采用无机材料,一般为功函数较高的金属或金属氧化物,本发明优选氧化铟锡(以下简称ITO)。
空穴注入材料一般采用聚噻吩/聚乙烯基苯磺酸钠(以下简称PEDOT:PSS)、酞菁铜(CuPc)和4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺(m-MTDATA),本发明优选聚噻吩/聚乙烯基苯磺酸钠(PEDOT:PSS)。
空穴传输层一般采用三芳胺类材料,如N,N’-二(1-萘基)-N,N′-二苯基-1,1-联苯基-4,4-二胺(NPB),4,4′,4″-三(N-咔唑)三苯胺(TCTA),或者本发明所述的材料;有机发光层种类较多,如蒽、芘、芴、苯乙烯基苯化合物、金属螯合物或聚合物材料等,发光层可以是单个发光材料,也可以是主体材料与掺杂材料的组合,常见的有三(8-羟基喹啉)铝,9,10-二(2-萘基)蒽。
电子传输层一般为金属有机配合物,如三(8-羟基喹啉)铝,也可以是苯并咪唑类,如1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TBPI)等;电子注入材料一般采用无机氟化物,如氟化锂(LiF),氟化铯(CsF),本发明优选氟化锂(LiF)。
阴极层一般采用锂、镁、钙、锶、铝或铟等功函数较低的金属或它们中的任一种与铜、金或银的合金。
本发明的器件制备方法如下:
(1)清洗阳极ITO。用清洗剂、去离子水和有机溶液分几步清洗带有阳极的玻璃基片;
(2)制备空穴注入层。通过旋涂或蒸镀方法,制备器件的空穴注入层;
(3)制备空穴传输层。通过旋涂或蒸镀方法,制备器件的空穴传输层;
(4)制备发光层。通过旋涂或蒸镀方法,制备器件的发光层;
(5)制备电子传输层。通过旋涂或蒸镀方法,制备器件的电子传输层;
(6)制备电子注入层。通过旋涂或蒸镀方法,制备器件的电子注入层;
(7)制备阴极。通过蒸镀或溅射的方法,制备金属阴极。
在现有的二胺化合物中,对三联苯类-4,4’-二基衍生物的芳香胺化合物由于具有空间障碍性,故分子间的相互作用小,而且,本发明提供的这类芳香胺化合物结构对称,容易合成,分子量较高使得化合物的玻璃化温度高,稳定性好,能够很好地克服常见对称化合物容易结晶的问题,使材料更易成膜提高制造器件的成品率,延长有机EL器件的寿命, 尤其是与蓝色发光材料组合效果更佳;此外,分子结构中引入烷基链能够提高化合物的溶解度,引入吸电子基如氰基和氟原子能够提高EA值拉低LUMO能级,进而降低化合物的能隙,即本发明涉及的芳香胺化合物可以通过取代基的引入设计方便调控化合物的能级,更有利于将其应用到有机EL器件中。
附图说明
图1是器件1、器件2、器件3、器件4以及对比化合物NPB的流明效率和亮度图;
图2是器件1、器件2、器件3、器件4以及对比化合物NPB的电流效率和亮度图。
具体实施方式
下面通过具体实施例,对本发明作进一步的说明,但本发明并不局限于此。
下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
中间体合成实施例1(中间体M1的合成)
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-12
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 4,4”-溴对三联苯、1mmol二(对三联苯)胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,为M1。
中间体合成实施例2(中间体M2的合成)
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-13
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二甲基-4,4”-二溴-1,1’:4’,1”-三联苯、1mmol二(对三联苯)胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,为M2。
中间体合成实施例3(中间体M3的合成)
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-14
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二氟-4,4”-二溴-1,1’:4’,1”-三联苯、1mmol二(对三联苯)胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,为M3。
中间体合成实施例4(中间体M4的合成)
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-15
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2’-二氟-4,4”-二溴-1,1’:4’,1”-三联苯、1mmol二(对三联苯)胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,为M4。
中间体合成实施例5(中间体M5的合成)
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-16
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二甲基-4,4”-二溴-1,1’:4’,1”-三联苯、1mmol二联苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,为M5。
合成实施例1
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-17
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 4,4”-二碘对三联苯、2mmol的二对三联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H1。1H NMR(500 MHz,Chloroform)δ8.16(8H),7.92(8H),7.59(12H),7.54(8H),7.44(4H),7.35(4H),7.25(20H)。
合成实施例2
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-18
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol联苯基对三联苯基胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H2。1H NMR(500 MHz,Chloroform)δ8.12(6H),7.71(16H),7.56(6H),7.51(6H),7.38(10H),7.30(10H),7.17(2H),7.13(2H),7.04(2H)。
合成实施例3
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-19
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol二(3,5-二甲基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至温室后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H4。1H NMR(500 MHz,Chloroform)δ7.99(4H), 7.79(6H),7.59(4H),7.55(4H),7.45(16H),7.41(2H),7.35(4H),7.24(6H),7.05(2H),6.99(4H),2.46(12H)。
合成实施例4
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-20
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol二(3-乙基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H12。1H NMR(500MHz,Chloroform)δ8.08(10H),7.59(4H),7.55(4H),7.45(12H),7.40(2H),7.35(10H),7.24(2H),7.10(2H),7.05(2H),6.96(2H),2.42(4H),1.24(6H)。
合成实施例5
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-21
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol二(3-叔丁基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H122。1H NMR(500MHz,Chloroform)δ8.12(4H),7.93(4H),7.82(6H),7.54(4H),7.46(14H),7.35(8H),7.24(10),7.06(2H),6.84(2H),1.21(18H)。
合成实施例6
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-22
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol二(3-环己基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H121。1H NMR(500MHz,Chloroform)δ8.13(4H),8.04(4H),7.82(6H),7.55(4H),7.47(8H),7.34(4H),7.27(2H),7.23(4H),7.12(6H),7.09(4H),7.03(2H),6.89(2H),2.50(2H),1.76(4H),1.60(12H),1.49(4H)。
合成实施例7
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-23
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol二(3-氟-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H22。1H NMR(500MHz,Chloroform)δ8.28(4H),8.18(4H),7.86(6H),7.55(4H),7.46(16H),7.40(4H),7.35(4H),7.24(4H),7.19(2H),7.11(2H),7.06(2H),6.91(2H)。
合成实施例8
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-24
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M1,1mmol二(3-氰基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H123。1H NMR(500 MHz,Chloroform)δ8.03(4H),7.72(6H),7.67(4H),7.60(10H),7.54(8H),7.44(10H),7.39(2H),7.36(2H),7.32(4H),7.28(2H),7.06(2H)。
合成实施例9
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-25
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M2,1mmol二联苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H29。1H NMR(500 MHz,Chloroform)δ8.13(4H),8.09(4H),7.66(8H),7.61(4H),7.54(6H),7.47(8H),7.41(4H),7.33(6H),7.25(4H),7.14(2H),7.06(2H),2.57(6H)。
合成实施例10
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-26
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M2,1mmol二(3-异丙基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H39。1H NMR(500 MHz,Chloroform)δ8.71(4H),8.00(4H),7.84(4H),7.69(1H),7.54(4H),7.50(1H),7.45(10H),7.41(2H),7.34(12H),7.25(6H),7.08(1H),6.97(1H),6.92(2H),2.78(2H),2.61(3H),2.49(3H),1.20(12H)。
合成实施例11
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-27
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M2,1mmol二(3-甲基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H30。1H NMR(500 MHz,Chloroform)δ8.20(4H),8.02(4H),7.55(4H),7.44(12H),7.35(9H),7.27(1H),7.21(4H),7.06(3H),7.02(1H),6.94(2H),6.88(1H),2.69(3H),2.59(3H),2.48(6H)。
合成实施例12
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-28
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M2,1mmol二(3-环戊基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H129。1H NMR(500MHz,Chloroform)δ8.25(4H),8.07(4H),7.68(1H),7.62(4H),7.55(8H),7.49(1H),7.46(10H),7.40(2H),7.33(12H),7.18(2H),7.06(1H),6.95(1H),6.91(2H),2.65(2H),2.60(3H),2.48(3H),1.92(4H),1.78(4H),1.68(8H)。
合成实施例13
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-29
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M2,1mmol二(3-氟-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H33。1H NMR(500MHz,Chloroform)δ8.30(4H),8.12(4H),8.06(4H),7.71(1H),7.54(4H),7.51(1H),7.48(1H),7.44(12H),7.36(4H),7.33(4H),7.24(4H),7.15(2H),7.08(1H),6.97(1H),6.88(2H),2.63(3H),2.51(3H)。
合成实施例14
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-30
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M2,1mmol二(3-氰基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H41。1H NMR(500MHz,Chloroform)δ7.98(4H),7.84(4H),7.69(5H),7.59(10H),7.54(8H),7.50(1H),7.47(2H),7.45(6H),7.40(2H),7.34(8H),7.07(1H),6.92(1H),2.62(3H),2.50(3H)。
合成实施例15
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-31
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M3,1mmol二(3-甲基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H126。1H NMR(500MHz,Chloroform)δ8.58(4H),8.09(4H),7.99(4H),7.80(1H),7.74(4H),7.55(4H),7.51(4H),7.43(10H),7.32(4H),7.28(4H),7.23(1H),7.19(1H),7.15(2H),7.04(2H),6.91(2H),6.84(1H),2.51(6H)。
合成实施例16
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-32
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M4,1mmol二(3-甲基-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H 125。1H NMR(500MHz,Chloroform)δ8.11(4H),7.92(1H),7.83(4H),7.75(1H),7.68(1H),7.62(4H),7.54(5H),7.45(10H),7.39(2H),7.33(6H),7.28(2H),7.24(5H),7.08(5H),6.97(2H),2.48(6H)。
合成实施例17
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-33
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M5,1mmol二联苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H 130。1H NMR(500MHz,Chloroform)δ7.78(8H),7.73(2H),7.69(8H),7.50(10H),7.41(4H),7.37(4H),7.35(8H),7.25(2H),2.62(6H)。
合成实施例18
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-34
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M5,1mmol联苯基三联苯基胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H 131。1H NMR(500MHz,Chloroform)δ8.89(2H),8.37(2H),8.10(2H),7.72(6H),7.50(18H),7.41(4H),7.34(6H),7.30(6H),7.24(2H),7.13(2H),2.58(6H)。
合成实施例19
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-35
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol M5,1mmol二(3-氟-4-苯基)苯胺,0.05%mmol的醋酸钯,0.2mmol特叔丁基膦,15mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H 132。1H NMR(500MHz,Chloroform)δ8.51(4H),7.89(4H),7.71(2H),7.56(1H),7.51(4H),7.45(13H),7.39(10H),7.30(3H),7.22(1H),6.97(2H),2.66(3H),2.63(3H)。
合成实施例20
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-36
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二氰基-4,4”-二溴-1,1’:4’,1”-三联苯,2mmol二联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H79。1H NMR(500MHz,Chlorororm)δ8.00(2H),7.87(2H),7.78(8H),7.71(8H),7.69(2H),7.49(8H),7.40(8H),7.34(8H)。
合成实施例21
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-37
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二氟-4,4”-二溴-1,1’:4’,1”-三联苯,2mmol二联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H127。1H NMR(500MHz,Chloroform)δ8.06(8H),7.75(10H),7.50(10H),7.40(8H),7.35(8H),7.19(2H)。
合成实施例22
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-38
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二环己基-4,4”-二溴-1,1’:4’,1”-三联苯,2mmol二联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H128。1H NMR(500MHz,Chloroform)δ8.05(8H),7.63(8H),7.56(2H),7.49(8H),7.40(6H),7.33(4H),7.26(8H),7.16(2H),2.67(1H),2.60(1H),2.04(2H),1.99(2H),1.74(3H),1.60(8H),1.51(2H),1.40(3H)。
合成实施例23
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-39
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”’-二甲基-4,4”’-二溴-1,1’:4’,1”:4”,1”’-四联苯,2mmol二联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H88。1H NMR(500MHz,Chloroform)δ7.83(2H),7.75(8H),7.67(2H),7.57(8H),7.50(8H),7.42(6H),7.33(8H),7.20(8H),2.70(6H)。
合成实施例24
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-40
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2”,3’二甲基-4,4”’-二溴-1,1’:4’,1”:4”,1”’-四联苯,2mmol二联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H113。1H NMR(500MHz,Chloroform)δ7.85(12H),7.74(2H),7.59(14H),7.49(8H),7.41(4H),7.34(8H),7.00(2H),2.50(6H)。
合成实施例25
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-41
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2’,4’-二甲基-3,3”-二溴-1,1’:4’,1”-三联苯,2mmol 4-三联苯-2-氰基-1,1’-联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H62。1H NMR (500MHz,Chloroform)δ8.21(4H),7.86(2H),7.75(6H),7.68(2H),7.58(8H),7.52(5H),7.45(9H),7.41(8H),7.24(8H),2.60(6H).
合成实施例26
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-42
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2’,2”,2”’-四甲基-4,4”’-二溴-1,1’:4’,1”:4”,1”’-四联苯,2mmol N-联苯基-2-叔丁基-联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H133。1H NMR(500MHz,Chloroform)δ8.53(2H),8.23(2H),7.92(2H),7.88(2H),7.85(2H),7.65(2H),7.59(2H),7.53(6H),7.47(12H),7.41(6H),7.34(2H),7.28(4H),7.15(2H),7.07(2H),7.04(2H),2.68(6H),2.58(6H),1.29(18H).
合成实施例27
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-43
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二甲基-4,4”-二溴-1,1’:4’,1”-三联苯,1mmol 3,3’-二异丙基-二联苯胺,1mmol 3,3’-二异丙基-1,1’:4’,1”-双三联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H40。1H NMR(500MHz,Chloroform)δ8.60(2H),8.30(2H),7.95(6H),7.69(1H),7.59(4H),7.52(5H),7.46(12H),7.33(12H),7.25(2H),7.08(1H),6.96(1H),6.92(2H),4.13(2H),2.78(2H),2.61(3H),2.48(3H),1.49(12H),1.18(12H).
合成实施例28
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-44
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2’,5’-二氰基-4,4”-二溴-1,1’:4’,1”-三联苯,1mmol双(2,6-二甲基联苯)胺,1mmol 3,3’-二异丙基-1,1’:4’,1”-双三联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲基重结晶得白色粉末,即为化合物H66。1H NMR(500MHz,Chloroform)δ8.32(2H),8.14(2H),7.97(4H),7.90(4H),7.64(2H),7.52(4H),7.44(16H),7.40(4H),7.25(2H),7.07(2H),6.99(4H),4.21(2H),2.46(12H),1.72(12H).
合成实施例29
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-45
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol2,5’-二甲基-4,4”-二溴-1,1’∶4’,1”-三联苯,1mmol N-联苯基-2-叔丁基-联苯胺,1mmol N-三联苯基-2’-叔丁基-联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H134。1H NMR(500MHz,Chloroform)δ8.78(2H),8.44(1H),8.32(2H),7.93(3H),7.87(2H),7.65(7H),7.51(15H),7.36(3H),7.25(13H),7.18(1H),7.05(2H),6.85(1H),2.61(6H),1.79(9H),1.20(9H).
合成实施例30
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-46
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2’,5’-二甲基-4,4”-二溴-1,1’∶4’,1”-三联苯,1mmol双(2,6-二甲基联苯)胺,1mmol 2,6-二甲基联苯-N-三联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H61。1H NMR(500MHz,Chloroform)δ8.36(2H),8.04(2H),7.86(2H),7.70(4H),7.60(4H),7.51(6H),7.43(16H),7.23(4H),7.05(2H),6.99(4H),3.90(6H),2.62(6H),2.46(12H).
合成实施例31
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-47
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,5’-二甲基-4,4”-二溴-1,1’∶4’,1”-三联苯,2mmol 2-异丙基联苯基-N-联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H55。1H NMR(500MHz,Chloroform)δ8.37(4H),8.07(2H),7.98(1H),7.87(1H),7.70(2H),7.60(5H),7.53(4H),7.47(8H),7.40(11H),7.35(2H),7.29(3H),6.94(1H),3.01(1H),2.78(1H),2.61(6H),1.21(12H).
合成实施例32
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-48
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”’-二乙基-4,4”’-二溴-1,1’∶4’,1”∶4”,1’”-四联苯,1mmol N-双(2-乙基-联苯)胺,1mmol N-双(2-环己基-联苯)胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H104。1H NMR(500MHz,Chloroform)δ7.73(3H),7.65(4H),7.61(1H),7.58(2H),7.49(13H),7.44(2H),7.29(13H),7.23(4H),7.13(1H),7.01(1H),6.91(2H),4.00(6H),3.07(4H),2.69(4H),2.43(1H),2.34(1H),1.88(2H),1.82(2H),1.73(3H),1.59(6H),1.40(5H),1.32(2H),1.27(6H).
合成实施例33
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-49
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2’,5”-二甲基-4,4”’-二溴-1,1’:4’,1”:4”,1”’-四联苯,1mmol N-双(2,6-二甲基-联苯)胺,1mmol 2-叔丁基-三联苯基-N-联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H119。1H NMR(500MHz,Chloroform)δ9.41(2H),9.37(2H),8.32(4H),8.27(2H),7.90(2H),7.85(2H),7.69(1H),7.65(3H),7.57(12H),7.47(7H),7.34(4H),7.21(3H),7.11(5H),7.00(4H),2.67(6H),2.50(12H),1.48(9H).
合成实施例34
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-50
氮气保护条件下,向50ml邻二甲苯溶剂依次加入1mmol 2,2”-二氰基-4,4”-二溴-1,1’:4’,1”-三联苯,1mmol 2-丁基联苯基-N-2-丁基联苯胺,1mmol 2-异丙基联苯基-N-2-异丙基联苯胺,0.1%mmol的醋酸钯,0.4mmol特叔丁基膦,30mmol叔丁醇钠,在100℃下反应4小时,降至室温后加入50ml水,萃取有机层,向有机层加入甲醇析出固体,甲苯重结晶得白色粉末,即为化合物H75。1H NMR(500MHz,Chloroform)δ8.75(1H),8.55(2H),8.24(4H),8.02(3H),7.94(1H),7.80(6H),7.70(1H),7.64(4H),7.60(2H),7.52(4H),7.41(11H),7.35(4H),7.29(1H),7.12(8H),7.03(4H),2.58(4H),1.69(12H),1.56(4H),1.39(4H),0.97(6H).
器件实施例1
有机EL器件可按下述方法制备:
(1)清洗阳极ITO。将涂布了ITO透明导电层的玻璃板在清洗剂中超声处理,在去离子水中冲洗,在丙酮与乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光清洗机照射10分钟,并用低能阳离子束轰击表面;
(2)制备空穴注入层。将PEDOT:PSS水溶液在一定转速下旋转涂布,然后在120℃退火15分钟,形成空穴注入层;
(3)制备空穴传输层。在空穴注入层之上,蒸镀一定厚度的含有式(H1)的化合物作为空穴传输层,蒸镀速率为0.1nm/s;
(3)制备发光层。在空穴传输层之上,蒸镀一定厚度的含有ADN和AlQ3的发光层,蒸镀速率为0.1nm/s;
(4)制备电子传输层。在发光层之上,蒸镀一定厚度的TPBI作为电子传输层,蒸镀速率为0.1nm/s;
(5)制备电子注入层。在电子传输层之上,蒸镀一定厚度的LiF作为电子传输层,蒸镀速率为0.1nm/s;
(6)制备阴极。在电子注入层之上,蒸镀一定厚度的Al作为阴极,蒸镀速率为0.1nm/s。
器件实施例2
除将式H2替换器件实施例1中的式H1,其他方式均按器件实施例1操作制备器件实施例2。
器件实施例3
除将式H29替换器件实施例1中的式H1,其他方式均按器件实施例1操作制备器件实施例3。
器件实施例4
除将式H79替换器件实施例1中的式H1,其他方式均按器件实施例1操作制备器件实施例4。
器件实施例5
除将式H62替换器件实施例1中的式H1,其他方式均按器件实施例1操作制备器件实施例5。
器件实施例6
除将式H104替换器件实施例1中的式H1,其他方式均按器件实施例1操作制备器件
实施例6。
比较实施例
除将NPB替换器件实施例1中的式H1,其他方式均按器件实施例1操作制备比较实施例。
[根据细则26改正11.11.2015] 
Figure WO-DOC-FIGURE-51
器件的实施例的寿命见表1。
表1
  HTL 寿命
器件实施例1 H1 10h
器件实施例2 H2 10h
器件实施例3 H29 9h
器件实施例4 H79 7h
器件实施例5 H62 7h
器件实施例6 H104 8h
比较实施例 NPB 4h
NPB的玻璃化温度不够高,容易在加电压出现结晶,导致寿命下降。从表格1可以看到,各项器件实施例的寿命均高于比较的NPB实施例,说明本发明的材料要比NPB的稳定性优于NPB,可以作为替代的空穴传输材料。
工业化的可行性
如以上详细说明所述,本发明的芳香胺化合物具有不易结晶,成膜性好,热稳定性高,容易合成的优点,可以制备长使用寿命的有机EL器件,具有极大的工业化可行性。

Claims (12)

  1. 一种具有通式I结构的化合物,
    Figure PCTCN2015091702-appb-100001
    其中,
    x为3或4;y1为1或2;y2为1或2;z1为1或2;z2为1或2;
    Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、含1-6碳原子的烷基或环烷基;
    a、b、c、d和e相同或不同,各自独立的表示0、1、2、3或4,且a>1时,Ry1可以为不同取代基,b>1时,Ry2可以为不同取代基;c>1时,Rz1可以为不同取代基;d>1时,Rz2可以为不同取代基;e>1时,Rx为相同取代基;
    其中,y1≥z1,y1≥z2;且当z1=z2=1时,Rx不能为氢原子,e不为0。
  2. 根据权利要求1所述的化合物,其特征在于,所述Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、环丙基、环丁基、环戊基或环己基。
  3. 根据权利要求1所述的化合物,其特征在于,所述Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、甲基、乙基、正丙基、异丙基、正丁基或叔丁基。
  4. 根据权利要求1所述的化合物,其特征在于,所述Rx、Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-CN、甲基、正丙基、异丙基、正丁基或叔丁基、环丙基、环丁基、环戊基或环己基。
  5. 根据权利要求1所述的化合物,其特征在于,所述化合物的相对分子量不超过1500。
  6. 根据权利要求5所述的化合物,其特征在于,所述化合物的相对分子量是850-1450。
  7. [根据细则26改正11.11.2015] 
    根据权利要求1所述的化合物,其特征在于,所述化合物选自由通式I-1至I-14所示化合物组成的组:
    Figure PCTCN2015091702-appb-100002

    Figure PCTCN2015091702-appb-100003

    Figure PCTCN2015091702-appb-100004

    Figure PCTCN2015091702-appb-100005

    Figure WO-DOC-FIGURE-1
    以及
    Figure WO-DOC-FIGURE-2

    其中,
    y1为1或2;y2为1或2;z1为1或2;z2为1或2;
    Ry1、Ry2、Rz1和Rz2相同或不同,各自独立的表示-H、-F、-CN、含1-6碳原子的烷基或环烷基;
    a、b、c和d相同或不同,各自独立的表示0、1、2、3或4,且a>1时,Ry1可以为相同或不同的取代基,b>1时,Ry2可以为相同或不同的取代基;c>1时,Rz1可以为相同或不同的取代基;d>1时,Rz2可以为相同或不同的取代基;
    其中,y1≥z1,y1≥z2
    前提是,在所述通式I-1中,当Ry1、Ry2、Rz1和Rz2表示-H时,y1=y2=z1=z2=2;y1=y2=z2=2且z1=1;或者y1=2且y2=z1=z2=1。
  8. [根据细则26改正11.11.2015] 
    根据权利要求7所述的化合物,其特征在于,所述芳香胺衍生物选自由如下化合物组成的组:
    Figure WO-DOC-FIGURE-3

    Figure WO-DOC-FIGURE-4

    Figure WO-DOC-FIGURE-5

    Figure WO-DOC-FIGURE-6

    Figure WO-DOC-FIGURE-7
  9. 一种有机电致发光器件,其特征在于,在所述有机电致发光器件的阴极和阳极之间夹有一层或多层有机薄膜层,所述一层或多层有机薄膜层中的至少一层含有单独的或作为混合物成分的根据权利要求1-8中任一项所述的化合物。
  10. 根据权利要求9所述的有机电致发光器件,其特征在于,所述权利要求1-8中任一项所述的化合物在所述有机电致发光器件中作为空穴传输材料或空穴注入材料。
  11. 根据权利要求9所述的有机电致发光器件,其特征在于,所述权利要求1-8中任一项所述的化合物在所述有机电致发光器件中作为主体材料。
  12. 根据权利要求9所述的有机电致发光器件,其特征在于,所述权利要求1-8中任一项所述的化合物在所述有机电致发光器件中作为蓝光材料。
PCT/CN2015/091702 2014-10-13 2015-10-12 芳香族胺衍生物及其有机电致发光器件 WO2016058504A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410539892.2 2014-10-13
CN201410539892.2A CN105566123B (zh) 2014-10-13 2014-10-13 芳香族胺衍生物及其有机电致发光器件

Publications (1)

Publication Number Publication Date
WO2016058504A1 true WO2016058504A1 (zh) 2016-04-21

Family

ID=55746130

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/091702 WO2016058504A1 (zh) 2014-10-13 2015-10-12 芳香族胺衍生物及其有机电致发光器件

Country Status (2)

Country Link
CN (1) CN105566123B (zh)
WO (1) WO2016058504A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021220952A1 (ja) * 2020-04-28 2021-11-04 東洋紡株式会社 含窒素複素環化合物及びその利用
US11617290B2 (en) 2015-12-22 2023-03-28 Samsung Display Co., Ltd. Organic light-emitting device
US11696496B2 (en) 2015-12-22 2023-07-04 Samsung Display Co., Ltd. Organic light-emitting device
US11937500B2 (en) 2015-12-22 2024-03-19 Samsung Display Co., Ltd. Organic light-emitting device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6810710B2 (ja) * 2016-01-14 2021-01-06 保土谷化学工業株式会社 有機エレクトロルミネッセンス素子

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007269738A (ja) * 2006-03-31 2007-10-18 Tdk Corp 有機el素子用化合物及び有機el素子
WO2014021572A1 (en) * 2012-07-31 2014-02-06 Sk Chemicals Co., Ltd. Compound for organic electroluminescent device and organic electroluminescent device including the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4667926B2 (ja) * 2005-03-30 2011-04-13 出光興産株式会社 芳香族アミン誘導体及びそれを用いた有機エレクトロルミネッセンス素子
CN102057514B (zh) * 2008-06-11 2016-03-30 保土谷化学工业株式会社 有机电致发光器件

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007269738A (ja) * 2006-03-31 2007-10-18 Tdk Corp 有機el素子用化合物及び有機el素子
WO2014021572A1 (en) * 2012-07-31 2014-02-06 Sk Chemicals Co., Ltd. Compound for organic electroluminescent device and organic electroluminescent device including the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11617290B2 (en) 2015-12-22 2023-03-28 Samsung Display Co., Ltd. Organic light-emitting device
US11696496B2 (en) 2015-12-22 2023-07-04 Samsung Display Co., Ltd. Organic light-emitting device
US11937500B2 (en) 2015-12-22 2024-03-19 Samsung Display Co., Ltd. Organic light-emitting device
WO2021220952A1 (ja) * 2020-04-28 2021-11-04 東洋紡株式会社 含窒素複素環化合物及びその利用

Also Published As

Publication number Publication date
CN105566123A (zh) 2016-05-11
CN105566123B (zh) 2018-03-23

Similar Documents

Publication Publication Date Title
JP6869402B2 (ja) 窒素含有化合物、有機エレクトロルミネッセンスデバイスおよび光電変換デバイス
JP6248159B2 (ja) 発光デバイス用のスピロビフルオレン化合物
JP7054537B2 (ja) 有機エレクトロルミネセント材料および素子
JP6307687B2 (ja) アミン誘導体、有機発光材料及びそれを用いた有機エレクトロルミネッセンス素子
WO2020135687A1 (zh) 一种含硼化合物及其制备方法和其应用
WO2016058504A1 (zh) 芳香族胺衍生物及其有机电致发光器件
TW201714869A (zh) 有機電激發光裝置及其材料
WO2020083327A1 (zh) 含螺二芴结构的有机化合物及其在oled器件中的应用
TW201730193A (zh) 具有螺環結構之化合物與包含其之有機發光裝置
CN110078755B (zh) 化合物、显示面板以及显示装置
JP2022530897A (ja) 化合物、それを含む有機エレクトロルミネッセンス素子及びその応用
US11532793B2 (en) Compound, display panel, and display apparatus
JP2023518759A (ja) 多環芳香族誘導体化合物を用いた有機発光素子
CN110256473B (zh) 一种化合物、有机光电装置和电子设备
KR20180066855A (ko) 신규한 아민계 화합물 및 이를 포함하는 유기 발광 소자
WO2021109819A1 (zh) 多取代螺二芴化合物、空穴传输材料组合物及光电器件
JP2023518069A (ja) 多環芳香族誘導体化合物を用いた有機発光素子
CN110551132A (zh) 一种含酮的化合物及其在有机电致发光器件上的应用
JP6381874B2 (ja) 有機エレクトロルミネッセンス素子用材料及びそれを用いた有機エレクトロルミネッセンス素子
WO2020135790A1 (zh) 一种含硼的化合物及其在有机电致发光器件上的应用
CN110759936A (zh) 化合物、显示面板以及显示装置
CN109134456B (zh) 一种并喹啉类衍生物及其应用和有机电致发光器件
CN113429397B (zh) 化合物、显示面板及显示装置
CN108727366B (zh) 苯并菲罗啉类衍生物及其应用
KR20140016214A (ko) 신규한 안트라센 유도체, 이의 제조방법 및 이를 이용한 유기전자소자

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15850375

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15850375

Country of ref document: EP

Kind code of ref document: A1