CN105968329B - 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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CN105968329B
CN105968329B CN201610505761.1A CN201610505761A CN105968329B CN 105968329 B CN105968329 B CN 105968329B CN 201610505761 A CN201610505761 A CN 201610505761A CN 105968329 B CN105968329 B CN 105968329B
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thiophene
base
bis
dicarboxylic acids
selenole
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CN105968329A (zh
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黄飞
马小娟
朱鹏
曹镛
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

本发明公开了一种含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，其结构式如下；本发明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：
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：
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：
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：
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：
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：
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：
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：
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：
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：
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：
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：
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＝8.5 Hz,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：
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：
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)：1HNMR(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：
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：
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
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 (1)

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的制备方法，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；
其中，R1为烷基链；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；
所述含电子给体单元D为如下结构的一种以上：
其中，R3、R4为氢原子，或者为其中一个或多个碳原子被氧原子、烯基、炔基、羟基、氨基、羰基、羧基、硝基、苯基或噻吩基取代的烷基链，或者其中一个或多个氢原子被卤素原子取代的烷基链。
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CN106977701A (zh) * 2017-03-21 2017-07-25 华南理工大学 含苯并二酰亚胺环的n型水醇溶性共轭聚合物及其在有机/聚合物光电器件中的应用
CN106977704A (zh) * 2017-03-31 2017-07-25 华南理工大学 一种含三唑并异吲哚‑5,7（2h，6h）‑二酮单元的三元共聚物及其制备方法与应用
CN112876657B (zh) * 2021-01-18 2022-08-09 合肥工业大学 一种高延展性的高性能半导体共轭聚合物及其制备方法
CN115612068A (zh) * 2022-09-30 2023-01-17 武汉工程大学 一类卤代噻唑类宽带隙聚合物及其在光电器件中的应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050940A (zh) * 2011-01-28 2011-05-11 华南理工大学 含6-R基-[1,2,5]噻唑[3,4-g]苯并三唑的有机半导体材料及其应用
CN103502228A (zh) * 2011-04-28 2014-01-08 默克专利股份有限公司 新颖光敏聚合物
CN105324460A (zh) * 2013-06-21 2016-02-10 默克专利有限公司 共轭聚合物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2011115113A (ru) * 2008-09-19 2012-10-27 Мерк Патент ГмбХ (DE) Полимеры, производные бис(тиеноциклопента)бензотиадиазола, и их применение в качестве органических полупроводников
CN101550234B (zh) * 2009-05-13 2012-12-26 中国科学院上海微系统与信息技术研究所 对苯胺类化合物有传感功能的荧光传感材料、方法及应用
CN101712674B (zh) 2009-11-13 2015-03-11 华南理工大学 烷基取代-s,s-二氧-二苯并噻吩单体及其制备方法与聚合物
CN101775123B (zh) * 2009-12-31 2012-05-23 华南师范大学 一种c9位侧链带有噻吩等芳杂环的聚芴共轭聚合物及其制备方法和应用
ITMI20111268A1 (it) * 2011-07-07 2013-01-08 Eni Spa Concentratore solare luminescente comprendente composti benzoselenadiazolici disostituiti
CN102718946A (zh) 2012-05-30 2012-10-10 华南理工大学 有机半导体聚合物及含有机半导体聚合物的太阳能电池
CN102746492A (zh) * 2012-06-25 2012-10-24 南京邮电大学 一种共轭主链掺杂的折线型水溶性聚芳撑乙炔及其制备方法
CN105968329B (zh) * 2016-06-28 2019-05-14 华南理工大学 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050940A (zh) * 2011-01-28 2011-05-11 华南理工大学 含6-R基-[1,2,5]噻唑[3,4-g]苯并三唑的有机半导体材料及其应用
CN103502228A (zh) * 2011-04-28 2014-01-08 默克专利股份有限公司 新颖光敏聚合物
CN105324460A (zh) * 2013-06-21 2016-02-10 默克专利有限公司 共轭聚合物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"1,3-Benzothiadiazole-5,6-Dicarboxylic Imide–A Versatile Building Block for Additive- and Annealing-Free Processing of Organic Solar Cells with Effi ciencies Exceeding 8%";Christian B.Nielsen等;《Advanced Materials》;20150204;第27卷(第5期);第948-953页
"2,1,3-Benzothiadiazole-5,6-dicarboxylic imide based low-bandgap 2,1,3-Benzothiadiazole-5,6-dicarboxylic imide based low-bandgap";Bin Yao等;《Organic Electronics》;20150804;第26卷;第305-313页

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