WO2020098150A1 - 一种热活化延迟荧光深红光高分子材料及其制备方法 - Google Patents

一种热活化延迟荧光深红光高分子材料及其制备方法 Download PDF

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WO2020098150A1
WO2020098150A1 PCT/CN2019/071996 CN2019071996W WO2020098150A1 WO 2020098150 A1 WO2020098150 A1 WO 2020098150A1 CN 2019071996 W CN2019071996 W CN 2019071996W WO 2020098150 A1 WO2020098150 A1 WO 2020098150A1
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monomer compound
red light
thermally activated
activated delayed
polymer material
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罗佳佳
李先杰
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Definitions

  • the invention belongs to the technical field of organic photoelectric materials, in particular to a thermally activated delayed fluorescent deep red light polymer material and a preparation method thereof.
  • Organic light emitting diode (Organic Light Emitting Diode, OLED for short) is a current-driven light-emitting device that uses organic materials as active materials. It specifically refers to organic semiconductor materials and organic light-emitting materials driven by an electric field through carrier injection and Recombination leads to luminous technology. Unlike inorganic materials, organic materials have the characteristics of low synthesis cost, adjustable function, flexibility and good film formation.
  • Photoelectric conversion efficiency is one of the important parameters for evaluating OLEDs. Since the advent of organic light-emitting diodes, various luminescent material systems based on fluorescence and phosphorescence have been developed to improve the luminous efficiency of organic light-emitting diodes.
  • the OLED of the fluorescent material has the characteristics of high stability, but it is limited by the law of quantum statistics. Under the action of electrical activation, the ratio of the singlet excited state excitons to the triplet excited state excitons is 1: 3, so the fluorescent material The quantum efficiency of the internal electroluminescence is limited to 25%. Phosphorescent materials can use singlet excited state excitons and triplet excited state excitons at the same time due to the heavy atom's orbital coupling effect. The theoretical quantum efficiency of electron emission can reach 100%. But phosphorescent OLED materials mostly use precious metals, one is high cost, and the other is not environmentally friendly.
  • thermally activated delayed fluorescence (TADF) materials In order to overcome the shortcomings of these two materials, Adachi of Kyushu University in Japan proposed a new class of organic light-emitting materials, namely thermally activated delayed fluorescence (TADF) materials.
  • TADF thermally activated delayed fluorescence
  • RIST reverse intersystem crossing
  • Thermally activated delayed fluorescent materials have attracted the attention of many researchers due to their unique advantages.
  • the performance of thermal vapor deposition devices based on small molecule TADF materials has been comparable to devices based on phosphorescent heavy metal complexes, but vapor deposition materials will make the device The cost becomes very high.
  • Polymer thermally activated delayed fluorescent materials have obvious advantages in wet processing due to their good film-forming properties.
  • the polymer luminescent material uses the main chain as the main body, and the side chain connects the luminescent guests to form a luminescent system, which can effectively avoid phase separation.
  • the polymer has good thermodynamic stability and film-forming properties, and the device can be prepared by lower cost solution processing.
  • the object of the present invention is to provide a thermally activated delayed fluorescent deep red light polymer material and a preparation method and application thereof to solve the problem of low luminous efficiency of organic light emitting diodes in the prior art.
  • the present invention provides a thermally activated delayed fluorescent deep red light polymer material, whose structural formula is as follows:
  • the luminescent layer plays a leading role in organic electroluminescent devices, and the performance of the luminescent material is a key factor that determines the performance of the device.
  • the host and guest of the light-emitting layer adopt simple physical doping, inevitable phase separation occurs, and charge transfer complexes and exciplexes are easily formed, which affects the performance of the device.
  • the polymer light-emitting material is a light-emitting system formed by the main chain as the main body and the side chain connected to the light-emitting guest, which can effectively avoid phase separation.
  • the polymer has good thermodynamic stability and film-forming properties, and the device can be prepared by lower cost solution processing.
  • the thermally activated delayed fluorescence deep red light polymer material according to the present invention is a main chain polymerized TADF molecular structure, and the side chain is connected to an alkyl chain.
  • the TADF polymer material of this structure has excellent TADF characteristics and dissolution Sex. Correspondingly, it can use solution processing to prepare electroluminescent devices, and can achieve good device effects.
  • the structural formula of the monomer compound B is:
  • the present invention also provides a method for preparing the thermally activated delayed fluorescent deep red light polymer material according to the present invention, which includes the following steps:
  • the polymer product is placed in n-hexane and acetone for extraction, and then dried to obtain the thermally activated delayed fluorescent deep red light polymer material according to the present invention.
  • the molar mass ratio of the monomer compound A, the monomer compound B, palladium acetate and tri-tert-butylphosphine tetrafluoroborate is: (4-6) : (4 ⁇ 6): (1.5 ⁇ 2.5): (5 ⁇ 7).
  • the method for synthesizing the monomer compound A includes the following steps:
  • reaction solution was poured into ice water, and the solid was filtered by suction, dissolved in dichloromethane, spinned into silica gel, and purified by column chromatography to obtain the monomer compound A.
  • the method for synthesizing the monomer compound B includes the following steps:
  • reaction solution was poured into ice water, extracted with dichloromethane, the organic phases were combined, spinned into silica gel, and separated and purified by column chromatography to obtain the monomer compound B.
  • the present invention also provides an organic electroluminescent device, which includes a light-emitting layer, the light-emitting layer containing the thermally activated delayed fluorescent deep red light polymer material according to the present invention.
  • the organic electroluminescent device includes a glass and conductive glass (ITO) substrate layer, a hole transport and injection layer, the light emitting layer, an electron transport layer, and a cathode layer.
  • ITO glass and conductive glass
  • the beneficial effect of the present invention is that the present invention relates to a thermally activated delayed fluorescence deep red light polymer material main chain polymerization TADF molecular structure, the side chain is connected with an alkyl chain, so it has both excellent TADF It is also soluble, and electroluminescent devices can be prepared by solution processing.
  • the present invention also provides an organic electroluminescent device that uses the thermally activated delayed fluorescent deep red light polymer material as a light-emitting layer, which can improve the luminous efficiency of the device and the performance of the light-emitting device is more stable.
  • FIG. 1 is a distribution diagram of the highest electron-occupied orbit (HOMO) of a thermally activated delayed fluorescent deep red light polymer material according to an embodiment of the present invention
  • LOMO lowest electron-occupied orbit
  • 3 is a photoluminescence spectrum of a thermally activated delayed fluorescent deep red light polymer material provided by one embodiment of the present invention at room temperature, where the polymer is in the film;
  • FIG. 5 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present invention.
  • the invention provides a thermally activated delayed fluorescent deep red light polymer material, the structural formula of which is as follows:
  • the luminescent layer plays a leading role in organic electroluminescent devices, and the performance of the luminescent material is a key factor that determines the performance of the device.
  • the host and guest of the light-emitting layer adopt simple physical doping, inevitable phase separation occurs, and charge transfer complexes and exciplexes are easily formed, which affects the performance of the device.
  • the polymer light-emitting material is a light-emitting system formed by the main chain as the main body and the side chain connected to the light-emitting guest, which can effectively avoid phase separation.
  • the polymer has good thermodynamic stability and film-forming properties, and the device can be prepared by lower cost solution processing.
  • the thermally activated delayed fluorescence deep red light polymer material according to the present invention is a main chain polymerized TADF molecular structure, and the side chain is connected to an alkyl chain.
  • the TADF polymer material of this structure has excellent TADF characteristics and dissolution Sex. Correspondingly, it can use solution processing to prepare electroluminescent devices, and can achieve good device effects.
  • FIG. 1 and FIG. 2 show that, according to an embodiment of the present invention, a thermally activated delayed fluorescent deep red light polymer material whose theoretically calculated highest electron occupying orbit (HOMO) and the distribution of its lowest electron unoccupied orbit (LUMO).
  • HOMO theoretically calculated highest electron occupying orbit
  • LUMO lowest electron unoccupied orbit
  • the lowest singlet state (S1) and the lowest triplet energy level (T1), and the electrochemical energy level are shown in the following table:
  • FIG. 3 illustrates a photoluminescence spectrum of a thermally activated delayed fluorescent deep red light polymer material provided by one embodiment of the present invention at room temperature, where the polymer is in the film.
  • FIG. 4 illustrates a thermally activated delayed fluorescent deep red light polymer material provided by an embodiment of the present invention.
  • the transient photoluminescence of the polymer in the film where it is located spectrum At room temperature, the transient photoluminescence of the polymer in the film where it is located spectrum.
  • the thermally activated delayed fluorescence deep red light polymer material according to the present invention is synthesized from monomer compound A and monomer compound B, wherein
  • the structural formula of the monomer compound A is:
  • the structural formula of the monomer compound B is:
  • the monomer compound A is synthesized by the following synthetic route
  • it may include the following steps:
  • reaction solution was poured into 200 mL of ice water, suction filtered to obtain an off-white solid, dissolved in dichloromethane, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 1: 3) After separation and purification, 1.2 g of blue-white powder was obtained with a yield of 61%.
  • the monomer compound B is synthesized by the following synthetic route
  • it may include the following steps:
  • the thermally activated delayed fluorescent deep red light polymer material according to the present invention can be synthesized by the following synthetic route
  • it may include the following steps:
  • the obtained polymer was extracted in n-hexane for three days, then extracted in acetone for three days, and dried in vacuum to obtain 0.56 g of white flocculent polymer.
  • the rate is 52%.
  • the number average molecular weight of the polymer is 3.5 kg / mol, the weight average molecular weight is 5.8 g / mol, and the PDI is 1.66.
  • thermally activated delayed fluorescent deep red light polymer material according to the present invention can be used to form a light-emitting layer in an organic electroluminescent device.
  • the organic electroluminescent device of the present invention with a thermally activated delayed fluorescent deep red light polymer material as a light-emitting layer may include a glass and conductive glass (ITO) substrate layer 1, a hole-transporting and injection layer 2 (poly 3,4-ethylenedioxythiophene: polystyrene sulfonate, PEDOT: PSS), luminescent layer 3 (the delayed fluorescence deep red light polymer material according to the present invention), electron transport layer 4 (1, 3,5-tris (3- (3-pyridyl) phenyl) benzene Tm3PyPB), cathode layer 5 (lithium fluoride / aluminum).
  • ITO glass and conductive glass
  • PEDOT poly 3,4-ethylenedioxythiophene: polystyrene sulfonate
  • luminescent layer 3 the delayed fluorescence deep red light polymer material according to the present invention
  • electron transport layer 4 (1, 3,5-tris (3- (3-pyridyl)
  • the electroluminescent device can be manufactured according to a method known in the art, such as the method disclosed in the reference (Adv. Mater. 2003, 15, 277.).
  • the specific method is: spin-coating, PESOT: PSS, polymer light-emitting layer on the washed conductive glass (ITO) substrate in sequence, and then sequentially depositing TmPyPB, 1 nm LiF and 100 nm Al under high vacuum conditions.
  • ITO / PEDOT PSS (50nm) / Polymer (40nm) / TmPyPB (40nm) / LiF (1nm) / Al (100nm).
  • the performance measurement of the above electroluminescent device wherein the current-luminance-voltage characteristic of the device is performed by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a corrected silicon photodiode
  • the electroluminescence spectrum is measured by SPEX CCD3000 spectrometer of French JY company. All measurements are done in the room temperature atmosphere.

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Abstract

本发明提供了一种热活化延迟荧光(Thermally Activated Delayed Fluorescence,TADF)深红光高分子材料，其是以主链聚合TADF分子结构，侧链连接烷基链，这种结构的TADF高分子材料具有优良的TADF特性以及溶解性。进一步的，本发明涉及的所述材料可使用溶液加工的方式来制备电致发光器件，并能取得良好的器件效果。

Description

一种热活化延迟荧光深红光高分子材料及其制备方法 技术领域
本发明属于有机光电材料技术领域，特别涉及一种热活化延迟荧光深红光高分子材料及其制备方法。
背景技术
有机发光二极管(Organic Light Emitting Diode，简称OLED)是一种以有机材料作为活性材料的电流驱动式发光器件，具体是指有机半导体材料和有机发光材料在电场的驱动下，通过载流子注入和复合导致发光的技术。与无机材料不同，有机材料具有合成成本低、功能可调、可柔性以及成膜性好的特点。
光电转换效率是评估OLED的重要参数之一，自有机发光二极管问世以来，为提高有机发光二极管的发光效率，各种基于荧光、磷光的发光材料体系被开发出来。荧光材料的OLED具有稳定性高的特点，但受限于量子统计学定律，在电激活作用下，产生的单重激发态激子和三重激发态激子的比例为1:3，因此荧光材料的内部电致发光量子效率被限制在25％。磷光材料由于具有重原子的旋轨耦合作用，可同时利用单重激发态激子和三重激发态激子，其理论内电子发光量子效率能够达到100％。但磷光的OLED材料多采用贵重金属，一是成本高，二是不环保。
为了克服这上述两种材料的缺点，日本九州大学的Adachi提出了一类新的有机发光材料，即热活化延迟荧光(TADF)材料。该类材料的单线态-三线态能隙非常小，三线态激子可以通过反向系间窜越(RIST)转变成单线态激子发光，因此器件的内量子效率可以达到100％。热活化延迟荧光材料以其独特的优势吸引了许多科研人员的关注，基于小分子TADF材料的热蒸镀器件的性能已经能够媲美基于磷光重金属配合物的器件，但是蒸镀型材料会使得器件的成本变得很高。
高分子热活化延迟荧光材料由于良好的成膜性，在湿法加工方面具有明显的优势。聚合物发光材料是以主链作为主体，侧链连接发光客体的方式形成发光体系，能够有效地避免相分离。同时，聚合物具有良好的热力学稳定性和成膜性，并且可通过成本较低的溶液加工的方式制备器件。
但是如何使得热活化延迟荧光高分子保持搞得光致发光量子产率以及较大的反向系间窜越常数仍然没有的到解决。目前可应用旋涂工艺制备电致发光器件的TADF材料屈指可数，TADF聚合物更是寥寥无几。
因此确有必要来开发一种TADF聚合物，以克服现有技术的缺陷。
技术问题
本发明的目的是提供一种热活化延迟荧光深红光高分子材料及其制备方法与应用，以解决现有技术中存在的有机发光二极管的发光效率低的问题。
技术解决方案
为实现上述目的，本发明提供一种热活化延迟荧光深红光高分子材料，其结构式如下：
Figure PCTCN2019071996-appb-000001
其中在有机电致发光器件中，起主导作用的为发光层，发光材料的性能是决定器件性能的关键因素。对于现有的小分子掺杂器件，其发光层的主客体采用简单的物理掺杂，不可避免的会存在相分离，且容易形成电荷转移复合物以及激基复合物，进而影响器件的性能。而聚合物发光材料则是是以主链作为主体，侧链连接发光客体的方式形成的发光体系，能够有效地避免相分离。同时，聚合物具有良好的热力学稳定性和成膜性，并且可通过成本较低的溶液加工的方式制备器件。
而本发明涉及的这种热活化延迟荧光深红光高分子材料，其是以主链聚合TADF分子结构，侧链连接烷基链，这种结构的TADF高分子材料具有优良的TADF特性以及溶解性。相应的，其可使用溶液加工的方式来制备电致发光器件，并能取得良好的器件效果。
进一步的，在不同实施方式中，其是由单体化合物A和单体化合物B合成的，其中所述单体化合物A的结构式为：
Figure PCTCN2019071996-appb-000002
所述单体化合物B的结构式为：
Figure PCTCN2019071996-appb-000003
进一步的，在不同实施方式中，其是由所述单体化合物A和单体化合物B通过下述合成路线合成的
Figure PCTCN2019071996-appb-000004
进一步的，在不同实施方式中，其中所述单体化合物A是通过下述合成路线合成出
Figure PCTCN2019071996-appb-000005
进一步的，在不同实施方式中，其中所述单体化合物B是通过下述合成路线合成出
Figure PCTCN2019071996-appb-000006
本发明的还提供了一种制备本发明涉及的所述热活化延迟荧光深红光高分子材料的制备方法，其包括以下步骤：
向反应瓶中加入所述单体化合物A、所述单体化合物B、醋酸钯和三叔丁基膦四氟硼酸盐；
在手套箱中加入NaOt-Bu和甲苯，在100～120℃反应40～60小时，冷却至室温；
使用甲醇和丙酮的混合溶剂中对上述反应产物进行沉降，得到的高分子产物；
将所述高分子产物放置在正己烷和丙酮中抽提，然后干燥得到本发明涉及的所述热活化延迟荧光深红光高分子材料。
进一步的，在不同实施方式中，其中所述所述单体化合物A、所述单体化合物B、醋酸钯和三叔丁基膦四氟硼酸盐的摩尔质量比为：(4～6)：(4～6)：(1.5～2.5)：(5～7)。
进一步的，在不同实施方式中，其中所述单体化合物A的合成方法包括以下步骤：
在氩气氛围下，向反应瓶中加入1-碘-3-氟-4-溴-苯腈和铜粉，抽通后打入除氧的甲苯，然后在100～120℃反应20～30小时，冷却至室温；
将反应液倒入冰水中，抽滤得固体，用二氯甲烷溶解，旋成硅胶，柱层析分离纯化，得到所述单体化合物A。
进一步的，在不同实施方式中，其中所述单体化合物B的合成方法包括以下步骤：
向反应瓶中加入3,3’-二己基-1,1’-二羟基二苯胺、氢氧化钾和催化剂，抽通后打入四氯化碳，100～120℃反应20～30小时，冷却至室温；
将反应液倒入冰水中，使用二氯甲烷萃取，合并有机相，旋成硅胶，柱层析分离纯化，得到所述单体化合物B。
本发明还提供了一种有机电致发光器件，，其包括发光层，所述发光层含有本发明涉及的所述热活化延迟荧光深红光高分子材料。
其中，所述有机电致发光器件包括玻璃和导电玻璃(ITO)衬底层，空穴传输和注入层、所述发光层、电子传输层以及阴极层。
有益效果
相对于现有技术，本发明的有益效果在于：本发明涉及的一种热活化延迟荧光深红光高分子材料主链聚合TADF分子结构，侧链连接烷基链，因此其既具有优良的TADF又具有溶解性，可使用溶液加工的方式制备电致发光器件。
进一步的，本发明还提供的一种有机电致发光器件，采用所述热活化延迟荧光深红光高分子材料作为发光层，能够提高器件的发光效率，发光器件性能更稳定。
附图说明
图1为本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，经过理论计算得出的其的最高电子占据轨道(HOMO)的分布图；
图2为本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，经过理论计算得出的其的最低电子占据轨道(LOMO)的分布图；
图3为本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，在室温下，其高分子在所在薄膜中的光致发光光谱；
图4为本本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，在室温下，其高分子在所在薄膜中的瞬态光致发光光谱；
图5为本发明涉及的一个实施方式提供的一种有机电致发光器件的结构示意图。
本发明的最佳实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供一种热活化延迟荧光深红光高分子材料，其结构式如下：
Figure PCTCN2019071996-appb-000007
其中在有机电致发光器件中，起主导作用的为发光层，发光材料的性能是决定器件性能的关键因素。对于现有的小分子掺杂器件，其发光层的主客体采用简单的物理掺杂，不可避免的会存在相分离，且容易形成电荷转移复合物以及激基复合物，进而影响器件的性能。而聚合物发光材料则是是以主链作为主体，侧链连接发光客体的方式形成的发光体系，能够有效地避免相分离。同时，聚合物具有良好的热力学稳定性和成膜性，并且可通过成本较低的溶液加工的方式制备器件。
而本发明涉及的这种热活化延迟荧光深红光高分子材料，其是以主链聚合TADF分子结构，侧链连接烷基链，这种结构的TADF高分子材料具有优良的TADF特性以及溶解性。相应的，其可使用溶液加工的方式来制备电致发光器件，并能取得良好的器件效果。
其中请参阅图1和图2所示，其图示了，本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，经过理论计算得出的其最高电子占据轨道(HOMO)的分布，以及其最低电子未占据轨道(LUMO)的分布。
进一步的，所述高分子热活化延迟荧光材料的分子中，其最低单重态(S1)和最低三重态能级(T1)，电化学能级如下表所示：
Figure PCTCN2019071996-appb-000008
请参阅图3所示，其图示了本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，在室温下，其高分子在所在薄膜中的光致发光光谱。
请参阅图4所示，其图示了本发明涉及的一个实施方式提供的一种热活化延迟荧光深红光高分子材料，在室温下，其高分子在所在薄膜中的瞬态光致发光光谱。
其中在一个实施方式中，本发明涉及的所述热活化延迟荧光深红光高分子材料，其是由单体化合物A和单体化合物B合成的，其中
所述单体化合物A的结构式为：
Figure PCTCN2019071996-appb-000009
所述单体化合物B的结构式为：
Figure PCTCN2019071996-appb-000010
其中所述单体化合物A是通过下述合成路线合成出
Figure PCTCN2019071996-appb-000011
具体的，在一个实施方式中，其可以是包括以下步骤：
向100mL二口瓶中加入1-碘-3-氟-4-溴-苯腈(3.25g，10mmol)，Cu粉(1.28g，20mmol)，抽通三次，在氩气氛围下打入50mL事先除氧的甲苯，然后在110℃反应24小时；
待反应冷却至室温，将反应液倒入200mL冰水中，抽滤得灰白色固体，用二氯甲烷溶解，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:3)分离纯化，得蓝白色粉末1.2g，产率61％。1H NMR(300MHz,CD2Cl2,δ):7.93(s,2H),7.59(s,2H).MS(EI)m/z:[M]+calcd for C14H4B2rF2N2,395.87；found,395.76.Anal.Calcd for C14H4B2rF2N2:C 42.25,H 1.01,N 7.04；found:C 42.28,H 1.07,N 6.93。
其中单体化合物B是通过下述合成路线合成出
Figure PCTCN2019071996-appb-000012
具体的，在一个实施方式中，其可以是包括以下步骤：
向100mL二口瓶中加入3,3’-二己基-1,1’-二羟基二苯胺(3.67g，10mmol)，KOH(1.12g，20mmol)，催化量的18-冠-6，抽通三次，加入50mL四氯化碳，在110℃反应24小时；
冷却至室温，将反应液倒入500mL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，得淡蓝色粉末1.6g，产率47％。1H NMR(300MHz,CD2Cl2,δ):7.2(s,2H),7.17(d,J＝6.9Hz,4H),7.09(s,4H),6.93(d,J＝6.3Hz,4H),2.53(m,J＝6.3Hz,8H),1.69-1.53(m,16H),1.43-1.29(m, 16H),0.88(t,J＝6.0Hz,12H).MS(EI)m/z:[M]+calcd for C49H66N2,682.52；found,682.50.Anal.Calcd for C49H66N2:C 86.16,H 9.74,N 4.10；found:C 86.11,H 9.65,N 4.09。
在得到所述单体化合物A和单体化合物B后，其可以通过以下合成路线合成出本发明涉及的所述热活化延迟荧光深红光高分子材料
Figure PCTCN2019071996-appb-000013
具体的，在一个实施方式中，其可以是包括以下步骤：
向200mL的反应瓶中加入单体化合物A(0.4g,1mmol)，单体化合物B(0.68g,1mmol)，醋酸钯(90mg，0.4mmol)和三叔丁基膦四氟硼酸盐(0.34g，1.2mmol)，然后在手套箱中加入NaOt-Bu(1.12g，12mmol)，加入50ml甲苯，在110℃下反应24小时；
冷却至室温，用250mL甲醇和30mL丙酮混合溶剂沉降，得到的高分子在正己烷里面抽提三天，接着在丙酮里抽提三天，真空干燥，得到白色的絮状高分子0.56g，产率52％。高分子的数均分子量为3.5kg/mol，重均分子量为5.8g/mol，PDI为1.66。
进一步的，本发明涉及的所述热活化延迟荧光深红光高分子材料可以用于构成有机电致发光器件中的发光层。
请参阅图5，本发明的热活化延迟荧光深红光高分子材料作为发光层的有机电致发光器件，可包括玻璃和导电玻璃(ITO)衬底层1，空穴传输和注入层2(聚3，4-乙撑二氧噻吩：聚苯乙烯磺酸盐，PEDOT:PSS)，发光层3(本发明涉及的所述延迟荧光的深红光高分子材料)，电子传输层4(1,3,5-三(3-(3-吡啶基)苯基)苯Tm3PyPB)，阴极层5(氟化锂/铝)。
电致发光器件可按本领域已知方法制作，如按参考文献(Adv.Mater.2003,15,277.)公开的方法制作。具体方法为：在经过清洗的导电玻璃(ITO)衬底上依次旋涂，PESOT:PSS， 高分子发光层，然后在高真空条件下依次蒸镀TmPyPB，1nm的LiF和100nm的Al。用该方法制得如图1所示的器件，各种具体的器件结构如下：
ITO/PEDOT:PSS(50nm)/高分子聚合物(40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)。
进一步的，对上述电致发光器件进行性能测量，其中所述器件的电流-亮度-电压特性是由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400Sourcemeter、Keithley 2000 Currentmeter)完成的，电致发光光谱是由法国JY公司SPEX CCD3000光谱仪测量的，所有测量均在室温大气中完成。其中所述器件的性能数据见下表：
Figure PCTCN2019071996-appb-000014
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明。

Claims (10)

  1. 一种热活化延迟荧光深红光高分子材料，其中，其结构式如下：
    Figure PCTCN2019071996-appb-100001
  2. 根据权利要求1所述的一种热活化延迟荧光深红光高分子材料，其中，其是由单体化合物A和单体化合物B合成的，其中
    所述单体化合物A的结构式为：
    Figure PCTCN2019071996-appb-100002
    所述单体化合物B的结构式为：
    Figure PCTCN2019071996-appb-100003
  3. 根据权利要求2所述的一种热活化延迟荧光深红光高分子材料，其中，其是由所述单体化合物A和单体化合物B通过下述合成路线合成的
    Figure PCTCN2019071996-appb-100004
  4. 根据权利要求2所述的一种热活化延迟荧光深红光高分子材料，其中，其中所述单体化合物A是通过下述合成路线合成的
    Figure PCTCN2019071996-appb-100005
  5. 根据权利要求2所述的一种热活化延迟荧光深红光高分子材料，其中，其中所述单体化合物B是通过下述合成路线合成的
    Figure PCTCN2019071996-appb-100006
  6. 一种制备权利要求1所述的热活化延迟荧光深红光高分子材料的制备方法，其中，包括以下步骤：
    向反应瓶中加入所述单体化合物A、所述单体化合物B、醋酸钯和三叔丁基膦四氟硼酸盐；
    在手套箱中加入NaOt-Bu和甲苯，在100～120℃反应40～60小时，冷却至室温；
    使用甲醇和丙酮的混合溶剂中对上述反应产物进行沉降，得到的高分子产物；
    将所述高分子产物放置在正己烷和丙酮中抽提，然后干燥得到本发明涉及的所述热活化延迟荧光深红光高分子材料。
  7. 如权利要求6所述的一种热活化延迟荧光深红光高分子材料的制备方法，其中，所述所述单体化合物A、所述单体化合物B、醋酸钯和三叔丁基膦四氟硼酸盐的摩尔质量比为：(4～6)：(4～6)：(1.5～2.5)：(5～7)。
  8. 如权利要求6所述的一种热活化延迟荧光深红光高分子材料的制备方法，其中，其中所述单体化合物A的合成方法包括以下步骤：
    在氩气氛围下，向反应瓶中加入1-碘-3-氟-4-溴-苯腈和铜粉，抽通后打入除氧的甲苯，然后在100～120℃反应20～30小时，冷却至室温；
    将反应液倒入冰水中，抽滤得固体，用二氯甲烷溶解，旋成硅胶，柱层析分离纯化，得到所述单体化合物A。
  9. 如权利要求6所述的一种热活化延迟荧光深红光高分子材料的制备方法，其中，其中所述单体化合物B的合成方法包括以下步骤：
    向反应瓶中加入3,3’-二己基-1,1’-二羟基二苯胺、氢氧化钾和催化剂，抽通后打入四氯化碳，在100～120℃反应20～30小时，冷却至室温；
    将反应液倒入冰水中，使用二氯甲烷萃取，合并有机相，旋成硅胶，柱层析分离纯化，得到所述单体化合物B。
  10. 一种有机电致发光器件，其包括发光层，其中，所述发光层含有权利要求1-5中任一项所述的热活化延迟荧光深红光高分子材料。
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