WO2018000735A1 - 含1,2,5-苯并硒二唑-n-r1-5,6-二元羧酸酰亚胺的聚合物及其制法与应用 - Google Patents

含1,2,5-苯并硒二唑-n-r1-5,6-二元羧酸酰亚胺的聚合物及其制法与应用 Download PDF

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WO2018000735A1
WO2018000735A1 PCT/CN2016/109097 CN2016109097W WO2018000735A1 WO 2018000735 A1 WO2018000735 A1 WO 2018000735A1 CN 2016109097 W CN2016109097 W CN 2016109097W WO 2018000735 A1 WO2018000735 A1 WO 2018000735A1
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group
dicarboxylic acid
benzoselenadiazole
thiophen
bis
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PCT/CN2016/109097
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French (fr)
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黄飞
马小娟
朱鹏
曹镛
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华南理工大学
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Priority to US15/545,321 priority Critical patent/US10090423B2/en
Publication of WO2018000735A1 publication Critical patent/WO2018000735A1/zh

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Definitions

  • the invention relates to the application of polymers in the field of optoelectronic materials and devices, in particular to a conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide and Its production method and application.
  • the organic solar cell active layer material has many kinds of materials and the chemical structure of organic molecules is easy to modify.
  • the preparation and purification of the compound are simple and convenient, and it can be made into a large-area flexible thin film device, which has the advantage of future cost. And the wide distribution of resources.
  • An organic solar cell can be prepared into a film, and a solar cell forming a flexible foldable substrate can be prepared to form a flexible solar cell.
  • Organic solar cells have the advantages of large manufacturing area, low cost, simplicity, and flexibility. Therefore, it has great commercial development and application prospects.
  • the development of organic solar conjugated molecular materials is insufficient.
  • each active layer material In order to achieve efficient photoelectric conversion, from the viewpoint of active layer materials, it is required that each active layer material has high efficiency absorption of sunlight and high carrier mobility. , resulting in high conversion efficiency. To achieve these goals, it is important to develop more new donor polymers.
  • the object of the present invention is to provide a 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid acyl group with high energy conversion efficiency in view of the shortcomings of the current development of novel conjugated molecular materials.
  • Another object of the present invention is to provide a process for the preparation and use of the above conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide.
  • a conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide the structural formula of which is:
  • x, y are the relative contents of the 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide unit and the electron donor unit D in the conjugated polymer;
  • the donor unit D is attached to the 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide in a conjugated manner, and n is the degree of polymerization of the conjugated polymer.
  • aromatic groups Ar 1 and Ar 2 are one or more of the following:
  • R 2 is a hydrogen atom or an alkyl chain, or one or more carbon atoms thereof are substituted by an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a phenyl group or a thiophene group. , or one or more of the hydrogen atoms are replaced by a halogen atom.
  • the electron donor unit D is one or more of the following structures:
  • R 3 and R 4 are a hydrogen atom or an alkyl chain, or one or more of the carbon atoms is an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, a nitro group, a phenyl group or A thiophene substituent, or one or more of the hydrogen atoms, is replaced by a halogen atom.
  • R 2 , R 3 , and R 4 are a linear, branched or cyclic alkyl chain having 1 to 30 carbon atoms.
  • the conjugated polymers described above are used in the preparation of a light-emitting layer of a polymer light-emitting diode device, preparation of a semiconductor active layer in a polymer field effect transistor, or preparation of an active layer of a polymer solar photovoltaic cell.
  • the present invention obtains a plurality of conjugated electron donor units by still coupling copolymerization with a 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide monomer.
  • the conjugated polymer of the 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide of the present invention can be produced by the following method:
  • step (2) 4,7-bis(thiophen-2-yl)-1,2,5-benzoselenadiazole-NR 1 -5,6-di can be converted by the adjustment of the D structure.
  • the meta-carboxylic acid imide derivative has good solution processability and photoelectric properties, and finally succeeds in the 4,7-bis(thiophen-2-yl)-1,2,5-benzoselenadiazole-NR 1 -5 , a 6-dicarboxylic acid imide structure is introduced into the polymer to prepare a series containing 4,7-di(thiophen-2-yl)-1,2,5-benzoselenadiazole-NR 1 -5, Conjugated polymer of 6-dicarboxylic acid imide.
  • the structures of small molecules and polymer materials were characterized by nuclear magnetic resonance (NMR), mass spectrometry (MS) and gel chromatography (GPC).
  • NMR nuclear magnetic resonance
  • MS mass spectrometry
  • GPC gel chromatography
  • the spectral properties of the polymer materials were tested by UV-visible spectrometer, and the prepared polymers were prepared.
  • Optoelectronic devices characterize their optoelectronic properties.
  • the 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide of the invention has a large volume of selenium atoms and a large number of electrons, so that the polymer containing selenium atoms is easy to red in the absorption spectrum. shift. It is expected to exhibit better narrow bandgap solar cell materials. It can be predicted that the conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide has good optical properties and is a kind of commercial application prospect. material.
  • a conjugated polymer material based on 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide is a promising photovoltaic material. So far, there have been no reports in this field.
  • the present invention synthesizes a conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide for the first time and is successfully applied to the field of optoelectronics.
  • the present invention has the following advantages:
  • the conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide has a novel structure and is original.
  • the conjugated polymer containing 1,2,5-benzoselenadiazole-NR 1 -5,6-dicarboxylic acid imide has various functions, and the benzoselenadiazole compound has a very low optical band. Gap and good stability.
  • the selenium atom has a larger radius and more electrons, so that the selenium-containing polymer is easily red-shifted in the absorption spectrum.
  • Figure 1 is a film absorption spectrum of the prepared polymer
  • Figure 2 is an absorption spectrum of the prepared polymer in a chlorobenzene solution.
  • 3 and 4 are electrochemical graphs of the prepared polymer.
  • Elemental analysis calculated: C, 73.71%; H, 6.68%; N, 2.93%; O, 2.23%; S, 8.94%; Se, 5.51%; Test value: C, 73.78%; H, 6.60%; N, 2.93%; O, 2.24%; S, 8.94%; Se, 5.51%.
  • reaction solution was precipitated into methanol, and then subjected to Soxhlet extraction with methanol, acetone and n-hexane, followed by the addition of an aqueous solution of sodium diethyldithiocarbamate trihydrate ( 225 mg, 1 mmol, 100 mL of water) was stirred at 60 ° C for 8 hours to remove the palladium catalyst in the reaction, which was subjected to Soxhlet extraction with methanol, acetone and n-hexane, and dried to give a dark green solid (202 mg), yield: 87.45%.
  • the solution was precipitated in methanol, and subjected to Soxhlet extraction with methanol, acetone and n-hexane, followed by the addition of an aqueous solution of sodium diethyldithiocarbamate trihydrate (225 mg, 1 mmol, 100 mL of water) at 60 ° C for 8 hours.
  • the palladium catalyst in the reaction was removed, and subjected to Soxhlet extraction with methanol, acetone and n-hexane, and dried to give a dark green solid (137 mg), yield: 85.09%.
  • Elemental analysis calculated: C, 66.51%; H, 6.64%; N, 4.01%; O, 3.06%; 12.25%; Se, 7.54%; Test value: C, 66.57%; H, 6.66%; N, 4.00%; O, 3.03%; S, 12.22%; Se, 7.52%. Mass spectrum: calculated: 1047.41; found: 1046.8.
  • Elemental analysis calculated: C, 64.12%; H, 5.64%; F, 3.27%; N, 3.62%; O, 5.51%; S, 11.04%; Se , 6.80%; Test value: C, 64.15%; H, 5.60%; F, 3.24%; N, 3.62%; O, 5.55%; S, 11.08%; Se, 6.76%.
  • the ultraviolet-visible absorption spectrum of the polymer prepared above is shown in Fig. 1 and Fig. 2, and the ultraviolet-visible absorption spectrum was measured on a Shimadzu UV-3600 ultraviolet analyzer.
  • the polymers P1, P2, and P3 have strong absorption at 400-500 nm and 600-800 nm.
  • the maximum absorption peaks of the polymers P1, P2 and P3 are 465 nm, 447 nm and 414 nm.
  • the maximum absorption peaks in chlorinated benzene are 457 nm, 438 nm and 406 nm, indicating that the above polymers have strong absorption of sunlight.
  • Table 1 shows the molecular orbital energy levels and optical band gaps of the above polymers.
  • the electrochemical curves of the polymer prepared above are shown in Fig. 3 and Fig. 4. It can be seen that the above polymer has a deep HOMO level (the HOMO level is the highest occupied molecular orbital, and the LUMO level is the lowest unoccupied molecular orbital). ). Among them, the polymers P1, P2, P3, P4, and P5 have deep HOMO levels. Due to the presence of selenium atoms, their optical band gaps are relatively narrow, consistent with the above table data. Therefore, the conjugated polymers of the present invention can be used to fabricate polymer light-emitting diode devices, polymer field effect transistors and polymer solar cells. Active layer.

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Abstract

一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物及其制法与应用，所制备的共轭聚合物具有荧光性，对太阳光有较宽的吸收，因此可用于制作聚合物发光二极管器件，聚合物场效应晶体管和聚合物太阳能电池的活性层。

Description

含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物及其制法与应用 技术领域
本发明涉及聚合物应用于光电子材料与器件领域，特别涉及一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物及其制法与应用。
背景技术
太阳能是一种绿色可再生资源，有机太阳能电池活性层材料的种类繁多且有机分子的化学结构容易修饰，化合物的制备提纯加工简便，可以制成大面积的柔性薄膜器件，拥有未来成本上的优势以及资源的广泛分布性。有机太阳能电池可制备成膜，并且可以制备形成可卷曲折叠的衬底上形成柔性的太阳能电池。有机太阳能电池具有制造面积大、廉价、简易、柔性等优点。因而具有巨大的商业开发和应用前景。但是，目前有机太阳能共轭分子材料种类开发不足，为了实现高效的光电转换，从活性层材料的角度上考虑，需要每个活性层材料对太阳光有高效率的吸收以及高载流子迁移率，从而得到高的转换效率。要实现这些目标，研制更多的新型给体聚合物就显得十分重要。
发明内容
本发明的目的在于针对目前新型共轭分子材料开发的不足，提供能量转换效率较高的一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺单元的聚合物材料。
本发明的另一目的在于提供所述的含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物的制备方法与应用。
本发明通过以下技术方案实现：
一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物，其结构式为：
Figure PCTCN2016109097-appb-000001
其中，R1为氢原子或烷基链；所述烷基链为具有1～24个碳原子的直链、支链或者环状烷基链，或其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代，氢原子被卤素原子或上述官能团取代；Ar1、Ar2为芳香基团；D为电子给体单元；所述n为1～10000的自然数，0<x<1,0<y<1,x+y＝1。x、y分别为所述共轭聚合物中1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺单元与电子给体单元D的相对含量；电子给体单元D与1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺以共轭方式相连，n为所述共轭聚合物的聚合度。
进一步地，所述芳香基团Ar1、Ar2为如下所述的一种或两种以上：
Figure PCTCN2016109097-appb-000002
其中，R2为氢原子或烷基链，或其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、硝基、苯基或噻吩取代基，或其中一个或多个氢原子被卤素原子取代。
进一步地，所述电子给体单元D为如下所示结构的一种或两种以上：
Figure PCTCN2016109097-appb-000003
Figure PCTCN2016109097-appb-000004
其中，R3、R4为氢原子或烷基链，或其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、硝基、苯基或噻吩取代基，或其中一个或多个氢原子被卤素原子取代。
更进一步地，所述R2、R3、R4为具有1～30个碳原子的直链、支链或者环状烷基链。
以上所述共轭聚合物在制备聚合物发光二极管器件的发光层、制备聚合物场效应晶体管中半导体活性层或制备聚合物太阳能光伏电池的活性层中应用。
本发明通过选择多种共轭电子给体单元分别与含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺单体进行still偶联共聚，获得含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物。
本发明1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物可采用如下方法制备：
(1)以2,5-二噻吩-3,4-并噻唑为母体，与丁炔二酸二甲酯反应，得到4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二甲酸二甲酯；再通过水解，得到4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二羧酸；然后与乙酸酐反应，得到4,8-二(噻吩-2-基)异苯并呋喃[5,6-C][1,2,5]噻二唑-5,7-二酮；然后与辛胺反应，得到6-辛基-4,8-二(噻吩-2-基) -5H-[1,2,5]噻二唑并[3,4-f]的异吲哚-5,7(6H)-二酮；再通过铁粉还原，得到5,6-二氨基-4,7-二(噻吩-2-基)-N-R1-异哚吲-1,3-二酮，再将5,6-二氨基-4,7-二(噻吩-2-基)-N-R1-异哚吲-1,3-二酮和二氧化硒进行反应，得到4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺，最后通过NBS溴化得到最终单体4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺。
(2)金属催化偶联反应：将含电子给体单元D的具有金属催化偶联反应活性官能团的单体与步骤(1)所得的4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺在金属催化剂下反应，得到初步功能化的含电子给体单元结构和4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物。
(3)在步骤(2)中可以通过D结构的调节变换使4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺衍生物具有良好的溶液加工性及光电性能，最终成功将4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺结构引入到聚合物中，制备系列含4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物。
通过核磁共振(NMR)、质谱(MS)和凝胶色谱(GPC)表征了小分子和聚合物材料的结构，通过紫外可见光谱仪测试聚合物材料的光谱性质，同时将所制得的聚合物制备成光电器件表征他们的光电性能。
本发明1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺中硒原子体积大，电子多，使得含硒原子的聚合物在吸收光谱中易于红移。有望展现出更好的窄带隙太阳电池材料。可以预测，含有1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物具有良好的光学性能，是一类具有商业化应用前景的材料。
2,5-二噻吩-3,4-并噻唑和1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的结构式如下：
Figure PCTCN2016109097-appb-000005
基于1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物材料作为一类有前途的光电材料。目前为止，在该领域未曾有人报道。本发明首次合成出了含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物并成功应用于光电领域。
与现有技术相比，本发明具有以下优点：
含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物结构新颖，具有独创性。含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物具有多种功能，苯并硒二唑类化合物有很低的光学带隙和好的稳定性。硒原子半径较大，电子更多，使得含硒原子的聚合物在吸收光谱中易于红移。由于其良好的溶液加工性能、优异的光电性能如带隙较窄，在制作聚合物发光二极管的发光层、聚合物场效应晶体管以及聚合物太阳能电池的活性层领域具有良好的应用。
附图说明
图1为所制备聚合物的薄膜吸收谱图；
图2为所制备聚合物在氯苯溶液中的吸收谱图。
图3、图4为所制备聚合物的电化学曲线图。
具体实施方式
为更好地理解本发明的内容，下面通过具体的实施例来进一步说明本发明的技术方案，具体包括合成、表征与器件制备，但不限于此。
实施例1
4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并噻二唑-N-R1-5,6-二元羧酸酰亚胺的制备路线及合成方法。
(1)4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二甲酸二甲酯的制备，合成路线如下：
Figure PCTCN2016109097-appb-000006
在250mL的三颈瓶中，氮气保护下，加入2,5-二噻吩-3,4-并噻唑(7.34g,23.99mmol)，丁炔二酸二甲酯(6.81g，47.97mmol)，再加入150mL二甲苯作溶剂，加热至110℃反应12小时。后处理：旋蒸，除去二甲苯，再加入DCM，拌硅胶粉，干法上柱。最终得到淡黄色固体产物5.6g。产率：59.01％。
(2)4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二羧酸的制备，合成路线与合成方法如下：
Figure PCTCN2016109097-appb-000007
在250mL的三颈瓶中，氮气保护下，加入4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二甲酸二甲酯(5.6g，13.46mmol)，加入150mL无水甲醇，再逐滴加入NaOH溶液(4.6mol/L,30mL)，加热至100℃反应12小时。后处理：在反应混合物中加入盐酸水溶液，搅拌数小时，过滤，得到黄色固体4.46g，产率：85％。
(3)4,8-二(噻吩-2-基)异苯并呋喃[5,6-C][1,2,5]噻二唑-5,7-二酮的制备，合成路线和合成方法如下：
Figure PCTCN2016109097-appb-000008
在250mL的三颈瓶中，氮气保护下，加入4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二羧酸(4.46g，11.49mmol)和33.92g乙酸酐，再加入160mL二甲苯作溶剂，加热至110℃反应12小时。后处理：旋蒸，加入无水乙醇然后过滤。得到黄色固体产物3.78g。产率：88％。
(4)6-辛基-4,8-二(噻吩-2-基)-5H-[1,2,5]噻二唑并[3,4-f]的异吲哚-5,7(6H)-二酮的制备，合成路线和合成方法如下：
Figure PCTCN2016109097-appb-000009
在500mL的三颈瓶中，氮气保护下，加入4,8-二(噻吩-2-基)异苯并呋喃[5,6-C][1,2,5]噻二唑-5,7-二酮(3.78g，10.22mmol)和辛胺(2.64g，20.42mmol)，再加入乙酸(180mL)，加热至100℃反应8小时，然后用注射器加入乙酸酐(70mL)，100℃下反应6小时。后处理:旋蒸，加入DCM溶解，干法上柱，最后重结晶，得到黄色固体产物3.97g。产率：78％。
(5)5,6-二氨基-4,7-二(噻吩-2-基)-N-辛基-异吲哚-1,3-二酮的制备，合成路线和合成方法如下：
Figure PCTCN2016109097-appb-000010
在250mL的三颈瓶中，氮气保护下，加入6-辛基-4,8-二(噻吩-2-基)-5H-[1,2,5]噻 二唑并[3,4-f]的异吲哚-5,7(6H)-二酮(3.97g，8.25mmol)和铁粉(5.54g，98.92mmol)，加入160mL乙酸作溶剂。加热至130℃反应4小时。后处理：将反应混合物加入至装有水的大烧杯中，吸出铁屑，然后过滤，待吹干后干法上柱。最终得到3.17g黄色固体，产率：85％。
(6)4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-辛基-5,6-二元羧酸酰亚胺的制备，合成路线和合成方法如下：
Figure PCTCN2016109097-appb-000011
在250mL的三口瓶中，氮气保护下，加入5,6-二氨基-2-辛基-4,7-二(噻吩-2-基)异吲哚-1,3-二酮(3.17g，7.00mmol)，加入80mL乙醇作溶剂，再加入二氧化硒(0.93g，8.40mmol)，加热至85℃反应12小时。后处理：旋蒸，重结晶。最终得到红色固体产物2.79g，产率：83％。
(7)4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并硒二唑-N-辛基-5,6-二元羧酸酰亚胺的制备，合成路线和合成方法如下：
Figure PCTCN2016109097-appb-000012
在150mL的三口瓶中，氮气保护下，加入6-辛基-4,8-二(噻吩-2-基)-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮(2.79g，5.28mmol)和NBS(2.16g，12.14mmol)，再加入100mL氯仿作溶剂，常温反应24小时。后处理：DCM萃取然后干法上柱。最终得到2.68g红色固体产物。产率：76％。核磁共振氢谱：(CDCl3)δ(ppm)：1H NMR(500MHz,CDCl3)δ7.68(d,J＝4.0Hz,2H),7.21(d,J＝4.0Hz,2H),3.78–3.65(m,2H),1.77 –1.60(m,2H),1.29(d,J＝17.7,8.6,4.6Hz,12H),0.86(t,J＝7.0Hz,4H).质谱：计算值：868.34；实测值：868.01。
实施例2
聚6辛基-4-(5-(4,4,9,9-四(4-甲氧苯基)-4,9-二氢-s-苯并二茚并[1,2-b:5,6-b']吡啶-2-基)噻吩-2-基)-8-(噻吩-2-基)-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮的制备，合成路线和合成步骤如下：
Figure PCTCN2016109097-appb-000013
氩气保护下，在10mL微波管内，加入4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并硒二唑-N-辛基-5,6-二元羧酸酰亚胺(103mg，0.15mmol)，(4,4,9,9-四(4-甲氧基苯基)-4,9-二氢-s-苯并二茚并[1,2-B：5,6-b']二-2,7-二基)双(三甲基锡烷)(185mg，0.15mmol)，四(三苯基膦)钯(8mg)和二甲苯(4mL)，微波200℃反应45min，待反应降至室温后将反应液沉析在甲醇中，先后用甲醇、丙酮、正己烷进行索氏抽提，然后加入二乙基二硫代氨基甲酸钠三水合物的水溶液(225mg，1mmol，100mL水)于60℃搅拌8小时，除去反应中的钯催化剂，用甲醇、丙酮、正己烷进行索氏抽提，干燥，得到深绿色固体(192mg)，产率：87.77％。核磁共振氢谱：(CDCl3)δ(ppm)：1H NMR(500MHz,CDCl3)δ7.89(d,J＝3.5Hz,2H),7.57(d,J＝9.8Hz,2H),7.24(s,2H),7.25(d,J＝8.1Hz,8H),7.16(d,J＝8.5Hz,8H),4.83(t,2H),2.55(p,J＝17.0Hz,8H),1.76–1.54(m,10H),1.43–1.06(m,34H),0.88(dd,J＝7.8,5.6Hz,15H).元素分析：计算值：C,73.71％；H,6.68％；N, 2.93％；O,2.23％；S,8.94％；Se,5.51％；测试值：C,73.78％；H,6.60％；N,2.93％；O,2.24％；S,8.94％；Se,5.51％。质谱：计算值：1461.99；实测值：1461.07。
实施例3
聚6辛基-4-(5-(4,4,9,9-四(4-甲氧苯基)-4,9-二氢-s-苯并二茚并二[1,2-b:5,6-b']吡啶-2-基)噻吩-2-基)-8-(噻吩-2-基)-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮的制备，合成路线和合成步骤如下：
Figure PCTCN2016109097-appb-000014
氩气保护下，在10mL微波管内，加入4,8-双(5-溴噻吩-2-基)-6-辛基-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮(103mg，0.15mmol)，IDTT(207mg，0.15mmol)，四(三苯基膦)钯(8mg)和二甲苯(4mL)，微波200℃反应45min，待反应降至室温后将反应液沉析在甲醇中，先后用甲醇、丙酮、正己烷进行索氏抽提，然后加入二乙基二硫代氨基甲酸钠三水合物的水溶液(225mg，1mmol，100mL水)于60℃搅拌8小时，除去反应中的钯催化剂，用甲醇、丙酮、正己烷进行索氏抽提，干燥，得到深绿色固体(202mg)，产率：87.45％。核磁共振氢谱：(CDCl3)δ(ppm)：1H NMR(500MHz,CDCl3)δ7.91(d,J＝3.5Hz,2H),7.77(t,2H),7.53(d,J＝9.8Hz,2H),7.29(s,2H),7.21(d,J＝8.1Hz,8H),7.12(d,J＝8.5Hz,8H),4.80(t,2H),2.58(p,J＝17.0Hz,8H),1.79–1.58(m,10H),1.47–1.13(m,34H),0.87(dd,J＝7.8,5.6Hz,15H).元素分析：计算值：C,71.47％； H,6.19％；N,2.72％；O,2.07％；S,12.44％；Se,5.11％；测试值：C,71.41％；H,6.19％；N,2.74％；O,2.07％；S,12.50％；Se,5.09％。质谱：计算值：1546.11；实测值：1540.78。
实施例4
聚4-(5-(5,10-十二烷基萘并[1,2-B：5,6-B']二噻吩-2-基)噻吩-2-基)-6-辛基-8-(噻吩-2-基)-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮的制备，合成路线和合成步骤如下：
Figure PCTCN2016109097-appb-000015
氩气保护下，在10mL微波管内，加入4,8-双(5-溴噻吩-2-基)-6-辛基-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮(103mg，0.15mmol)，5,10-二癸萘并[1,2-B：5,6-b']二-2,7-二基-双-三甲基锡烷(127mg，0.15mmol)，四(三苯基膦)钯(8mg)和二甲苯(3mL)，微波200℃反应45min，待反应降至室温后将反应液沉析在甲醇中，先后用甲醇、丙酮、正己烷进行索氏抽提，然后加入二乙基二硫代氨基甲酸钠三水合物的水溶液(225mg，1mmol，100mL水)于60℃搅拌8小时，除去反应中的钯催化剂，用甲醇、丙酮、正己烷进行索氏抽提，干燥，得到深绿色固体(137mg)，产率：85.09％。核磁共振氢谱：(CDCl3)δ(ppm)：1H NMR(500MHz,CDCl3)δ7.91(d,J＝3.5Hz,2H),7.53(d,J＝9.8Hz,2H),7.21(d,J＝8.1Hz,2H),7.12(d,J＝8.5Hz,2H),4.80(t,2H),2.58(p,J＝17.0Hz,2H),1.79–1.58(m,6H),1.47–1.13(m,38H),0.87(dd,J＝7.8,5.6Hz,9H).元素分析：计算值：C,66.51％；H,6.64％；N,4.01％；O,3.06％；S,12.25％；Se,7.54％； 测试值：C,66.57％；H,6.66％；N,4.00％；O,3.03％；S,12.22％；Se,7.52％。质谱：计算值：1047.41；实测值：1046.87。
实施例6
聚4-(5-(4,8-双(4-((2-乙基己基)氧基)-3-氟苯基)苯并[1,2-B：4,5-B']噻吩-2-基)噻吩-2-基)-6-辛基-8-(噻吩-2-基)-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮的制备，合成路线和合成步骤如下：
Figure PCTCN2016109097-appb-000016
氩气保护下，在10mL微波管内，加入4,8-双(5-溴噻吩-2-基)-6-辛基-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮(103mg，0.15mmol)，4,8-双(4-((2-乙基己基)氧基)-3-氟苯基)苯并[1,2-B：4,5-B']噻吩-2,6-二基-双-(三甲基锡烷)(144mg，0.15mmol)，四(三苯基膦)钯(8mg)和二甲苯(4mL)，微波200℃反应45min，待反应降至室温后将反应液沉析在甲醇中，先后用甲醇、丙酮、正己烷进行索氏抽提，然后加入二乙基二硫代氨基甲酸钠三水合物的水溶液(225mg，1mmol，100mL水)于60℃搅拌8小时，除去反应中的钯催化剂，用甲醇、丙酮、正己烷进行索氏抽提，干燥，得到深绿色固体(127mg)，产率：71.35％。核磁共振氢谱：(CDCl3)δ(ppm)：7.95(d,J＝3.5Hz,2H),7.50(d, J＝9.8Hz,2H),7.24(d,J＝8.1Hz,4H),7.12(d,J＝8.5Hz,4H),4.89(t,6H),2.52(p,J＝17.0Hz,4H),1.71–1.51(m,6H),1.42–1.11(m,26H),0.88(dd,J＝7.8,5.6Hz,15H).元素分析：计算值：C,64.12％；H,5.64％；F,3.27％；N,3.62％；O,5.51％；S,11.04％；Se,6.80％；测试值：C,64.15％；H,5.60％；F,3.24％；N,3.62％；O,5.55％；S,11.08％；Se,6.76％。质谱：计算值：1161.41；实测值：1160.36。
实施例7
聚4-(5-(4,8-双(3-氟-4-((2-己基癸基)氧基)苯基)苯并[1,2-B：4,5-B']噻吩-2-基)噻吩-2-基)-6-辛基-8-(噻吩-2-基)-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮的制备，合成路线和合成步骤如下：
Figure PCTCN2016109097-appb-000017
氩气保护下，在10mL微波管内，加入4,8-双(5-溴噻吩-2-基)-6-辛基-5H-[1,2,5]硒二唑并[3,4-f]的异吲哚-5,7(6H)-二酮(103mg，0.15mmol)，(4,8-双(3-氟-4-((2-己基癸)氧基)苯基)苯并[1,2-B：4,5-B']噻吩-2,6-二基)双(三甲基锡烷)(178mg，0.15mmol)，四(三苯基膦)钯(8mg)和二甲苯(4mL)，微波200℃反应45min，待反应降至室温后将反应液沉析在甲醇中，先后用甲醇、丙酮、正己烷进行索氏抽提，然后加入二乙基二硫代氨基甲酸钠三水合物的水溶液(225mg，1mmol，100mL水)于60℃搅拌8小时，除去反应中的钯催化剂，用甲醇、丙酮、正己烷进行索氏抽提，干燥，得到深绿色固体(169mg)，产率：81.64％。 核磁共振氢谱：(CDCl3)δ(ppm)：7.97(d,J＝3.5Hz,2H),7.56(d,J＝9.8Hz,2H),7.23(d,J＝8.1Hz,4H),7.18(d,J＝8.5Hz,4H),4.81(t,6H),1.75–1.53(m,6H),1.46–1.13(m,58H),0.87(dd,J＝7.8,5.6Hz,15H).元素分析：计算值：C,67.60％；H,7.05％；F,2.74％；N,3.03％；O,4.62％；S,9.26％；Se,5.70％；测试值：C,67.62％；H,7.01％；F,2.74％；N,3.07％；O,4.63％；S,9.26％；Se,5.67％。质谱：计算值：1385.84；实测值：1385.67。
上述制备的聚合物的紫外-可见光吸收光谱图如图1、图2所示，紫外-可见光吸收光谱在Shimadzu UV-3600紫外分析仪上测量。由图1和图2可以看出，聚合物P1、P2、P3在400-500nm、600-800nm有较强的吸收。其中聚合物P1、P2、P3的薄膜吸收最大峰在465nm，447nm，414nm，在氯化苯中的最大吸收峰在457nm,438nm，406nm，说明上述聚合物对太阳光有较强的吸收。同时，也表明上述聚合物由于硒原子的存在，在薄膜中容易发生红移。表1为上述聚合物的分子轨道能级和光学带隙。
表1
Figure PCTCN2016109097-appb-000018
上述制备的聚合物的电化学曲线如图3、图4所示，可以看出上述聚合物具有较深的HOMO能级(HOMO能级为最高占据分子轨道、LUMO能级为最低未占分子轨道)。其中聚合物P1、P2、P3、P4、P5具有较深的HOMO能级。由于硒原子的存在，它们的光学带隙相对都比较窄，与上表数据相符，因此，本发明的共轭聚合物可用于制作聚合物发光二极管器件，聚合物场效应晶体管和聚合物太阳能电池的活性层。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并任何不受上述实施例的限制，其他的未背离本发明的精神实质与原理下所做的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (5)

  1. 一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物,其特征在于，结构通式如下：
    Figure PCTCN2016109097-appb-100001
    其中，R1为氢原子或烷基链；所述烷基链为1～24个碳原子的直链、支链或者环状烷基链，或其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代，氢原子被卤素原子或氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基或硝基取代；Ar1、Ar2为芳香基团；D为电子给体单元；所述n为1～10000的自然数，0<x<1,0<y<1,且x+y＝1。
  2. 根据权利要求1所述的一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物，其特征在于，所述Ar1、Ar2为如下所述结构的一种以上：
    Figure PCTCN2016109097-appb-100002
    其中，R2为氢原子或烷基链，或其中一个或多个碳原子被氧原子、烯基、炔基、芳基、 羟基、氨基、羰基、羧基、硝基、苯基或噻吩取代基，或其中一个或多个氢原子被卤素原子取代；
    所述D为如下结构的一种以上：
    Figure PCTCN2016109097-appb-100003
    Figure PCTCN2016109097-appb-100004
    其中，R3、R4为氢原子或烷基链，或其中一个或多个碳原子被氧原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、硝基、苯基或噻吩取代基，或其中一个或多个氢原子被卤素原子取代。
  3. 根据权利要求2所述的一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物，其特征在于，所述R2、R3、R4为具有1～30个碳原子的直链、支链或者环状烷基链。
  4. 制备权利要求1-3任一项所述的一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物的方法，其特征在于，步骤如下：
    (1)以2,5-二噻吩-3,4-并噻唑为母体，与丁炔二酸二甲酯反应，得到4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二甲酸二甲酯；再通过水解，得到4,7-二(噻吩-2-基)苯并[c][1,2,5]噻二唑-5,6-二羧酸；然后与乙酸酐反应，得到4,8-二(噻吩-2-基)异苯并呋喃[5,6-C][1,2,5]噻二唑-5,7-二酮；然后与烷基胺反应，得到6-R1-4,8-二(噻吩-2-基)-5H-[1,2,5]噻二唑并[3,4-f]的异吲哚-5,7(6H)-二酮；再通过铁粉还原，得到5,6-二 氨基-4,7-二(噻吩-2-基)-N-R1-异哚吲-1,3-二酮，再将5,6-二氨基-4,7-二(噻吩-2-基)-N-R1-异哚吲-1,3-二酮和二氧化硒进行反应，得到4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺，最后通过NBS溴化得到最终单体4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺；
    (2)金属催化偶联反应：将含电子给体单元D的具有金属催化偶联反应活性官能团的单体与步骤(1)所得的4,7-二(5-溴-噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺在金属催化剂下反应，得到初步功能化的含电子给体单元结构和4,7-二(噻吩-2-基)-1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的共轭聚合物。
  5. 权利要求1所述的一种含1,2,5-苯并硒二唑-N-R1-5,6-二元羧酸酰亚胺的聚合物在制备聚合物发光二极管器件的发光层、制备聚合物场效应晶体管中的半导体活性层或制备聚合物太阳能光伏电池的活性层中的应用。
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