CN111205307A - 一种噻吩并苯并噻二唑二酮有机化合物、其制备方法与应用 - Google Patents

一种噻吩并苯并噻二唑二酮有机化合物、其制备方法与应用 Download PDF

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CN111205307A
CN111205307A CN202010125996.4A CN202010125996A CN111205307A CN 111205307 A CN111205307 A CN 111205307A CN 202010125996 A CN202010125996 A CN 202010125996A CN 111205307 A CN111205307 A CN 111205307A
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thienobenzothiadiazoledione
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葛子义
陈三辉
彭瑞祥
韩寓芳
严婷婷
宋伟
魏强
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

本发明提供一种噻吩并苯并噻二唑二酮有机化合物，其结构式如下：
Figure DDA0002394398470000011
其中，R1为C1‑C20烷基以及C1‑C20的烷氧基中的一种；Ar为噻吩、并二噻吩、并三噻吩、苯并二噻吩、吡咯并二噻吩、戊烷并二噻吩基团及其衍生物。该有机化合物具有带隙窄、平面性好以及刚性强等特点，通过聚合反应可作为有机光电活性给体材料。

Description

一种噻吩并苯并噻二唑二酮有机化合物、其制备方法与应用
技术领域
本发明属于有机化合物技术领域，具体涉及一种噻吩并苯并噻二唑二酮有机化合物、其制备方法与应用。
背景技术
有机太阳能电池由于其在低成本、易于大面积、柔性器件制备等上的巨大潜力，近几十年来备受关注。经过二十多年的发展，目前单层本体异质结的有机太阳能电池的效率已经达到16％以上，在未来将有更广大的前景。
发明内容
本发明提供一种噻吩并苯并噻二唑二酮有机化合物，具有带隙窄、平面性好，以及刚性强等特点，通过聚合反应可作为有机光电活性给体材料。
该有机化合物的结构式如下：
Figure BDA0002394398460000012
其中，R1为C1-C20烷基以及C1-C20的烷氧基中的一种；Ar为以下基团之一：
噻吩基团、噻吩衍生物基团、并二噻吩基团、并二噻吩衍生物基团、并三噻吩基、并三噻吩衍生物基团、苯并二噻吩基团、苯并二噻吩衍生物基团、吡咯并二噻吩基团、吡咯并二噻吩衍生物基团、戊烷并二噻吩基团、戊烷并二噻吩衍生物基团。
上述衍生物基团包括但不限于如下结构式(虚线为连接位置)：
Figure BDA0002394398460000011
上述各结构式中，R2为C1-C20的烷基，C1-C20的烷氧基、羰基、酯基、苯基、取代苯基、噻吩基、或取代噻吩基(C1-C20中含有羰基、酯基、苯基、取代苯基、噻吩基、取代噻吩基)。
本发明还提供一种制备上述苯并噻二唑二酮聚合物的方法，包括如下步骤：
(1)采用2,1,3-苯并噻二唑-4,7-二硼酸频那醇酯A和化合物B通过Suzuki偶联反应，得到中间体C，反应路线如下所示：
Figure BDA0002394398460000021
(2)中间体C与NBS反应，得到如下化合物D：
Figure BDA0002394398460000022
(3)化合物D和化合物E通过Stille偶联反应得到化合物F，反应路线如下所示：
Figure BDA0002394398460000023
(4)化合物F先进行水解反应，提纯后再和NBS(N-溴代丁二酰亚胺)反应得到如下化合物G：
Figure BDA0002394398460000024
(5)化合物G通过Friedel-Crafts反应得到如下所示的噻吩并苯并噻二唑二酮聚合物：
Figure BDA0002394398460000031
本发明在聚合物中引入醌式共轭结构单元，具有如下有益效果：
(1)该有机化合物具有良好的溶解性，易于加工成膜，经提纯后具有高的化学纯度；
(2)该有机化合物中引入二酮，增加了有机化合物分子的刚性和平面性；
(3)该有机化合物可与含锡单体化合物，例如PDBT、PDBT-2F、PDBT-2Cl等发生锡溴偶联聚合反应得到聚合物，该聚合物可作为有机光电活性给体材料，通过增长给体单元的π-π共轭长度使π-电子更有利于沿整个聚合物骨架分布，有利于载流子的迁移，与常用受体材料，例如IDIC、ITIC、Y6等有较好的能级匹配。
具体实施方式
下面结合实施例对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。
下述实施例中的所述试验方法，若无特殊说明，均为常规方法；所述材料和试剂，若无特殊说明，均可从商业途径获得。
实施例1：
本实施例中，噻吩并苯并噻二唑二酮SM1的化学结构如下：
Figure BDA0002394398460000032
该噻吩并苯并噻二唑二酮SM1的制备方法包括如下步骤：
(1)采用2,1,3-苯并噻二唑-4,7-二硼酸频那醇酯A和化合物B通过Suzuki偶联反应，得到中间体C，反应路线如下所示：
Figure BDA0002394398460000041
具体过程是：在三口瓶中加入化合物A和化合物B，然后加入中和剂碳酸钾、少量水和催化剂，催化剂为四三苯基膦钯，催化剂的加入量为化合物A的摩尔量的5％，化合物A和化合物B的摩尔比为1:2.3；再置换三次氮气，最后加入甲苯，在回流下反应18小时；反应结束后用旋蒸仪抽走溶剂，然后用三氯甲烷和水萃取，萃取后用无水硫酸钠干燥；旋干后，用石油醚过硅胶柱得到黄色油状物化合物C。
(2)中间体C与NBS反应，得到如下化合物D：
Figure BDA0002394398460000042
具体过程是：先将化合物C和N-溴代丁二酰亚胺在冰浴下反应15小时，再用三氯甲烷和水萃取，萃取后用无水硫酸钠干燥，最后用石油醚过柱得到黄色固体化合物D。
(3)化合物D和化合物E通过Stille偶联反应得到化合物F，反应路线如下所示：
Figure BDA0002394398460000043
具体过程是：先在三口瓶中加入化合物D和化合物E，再加入四三苯基膦钯作为催化剂，然后抽真空换氮气三次，最后加入甲苯，在回流下反应18小时；反应结束后用旋蒸仪抽走溶剂，然后用三氯甲烷和水萃取，萃取后用无水硫酸钠干燥；旋干后用石油醚过硅胶柱得到化合物F。
(4)化合物F先水解提纯后再和NBS得到如下化合物G：
Figure BDA0002394398460000051
具体过程是：先将化合物F和氢氧化钠按照摩尔比为1:10加入三口烧瓶中，然后加入少量乙醇，在70℃下反应15小时；反应结束后用三氯甲烷和水萃取，萃取后用无水硫酸钠干燥；旋干后后再投入到三口烧瓶中加入NBS冰浴反应12小时得到化合物G。
(5)通过Friedel-Crafts反应得到噻吩并苯并噻二唑二酮SM1：将化合物G和二氯亚砜溶剂(摩尔比为1:5)加入三口烧瓶中，在80℃反应12小时；反应结束后旋干溶剂，再准备一个将三口烧瓶和恒压滴液漏斗烘干，然后将旋干溶剂的化合物用超干二氯溶解倒入到三口烧瓶中，然后把恒压滴液漏斗组装在三口烧瓶上加入FeCl3，使整个装置抽真空换氮气三次，在三口烧瓶和恒压滴液漏斗中加入少许超干二氯溶剂，然后打开恒压滴液漏斗逐渐滴加到三口烧瓶中，在冰浴下反应15小时；反应结束后用三氯甲烷和水萃取，萃取后用无水硫酸钠干燥；旋干后过硅胶柱，用石油醚过柱，既得到噻吩并苯并噻二唑二酮的单体SM1。
将上述制得的单体SM1与含锡单体PDBT-2F发生锡溴偶联聚合反应得到聚合物，反应路线如下：
Figure BDA0002394398460000052
具体过程是：在25mL的两口瓶中，单体SM1和采用商业化材料PDBT-2F单体按照摩尔比1:1溶解在超干燥的氯苯(10mL)中，在氦气氛围循环抽放气除氧后，加入四三苯基磷钯并将混合物在120℃下避光搅拌12小时，反应结束后冷却至室温，加入到色谱纯甲醇中析出絮状物，收集固体在索氏提取器中。随后依次用甲醇，正己烷，氯仿抽提至无色。通过旋转蒸发仪旋干大部分溶剂后，再用色谱纯甲醇沉降，收集固体后真空干燥得到黑色聚合物SM2，产率85％。
将该聚合物SM2应用于太阳能电池。采用商业化的IDIC受体材料，按照ITO/PEDOT:PSS/SM2:IDIC/PDINO/Al制作太阳能电池。其中，活性层材料为SM2与IDIC，按照质量比SM2:IDIC为1:0.7混合在溶剂中，溶剂可以选用甲苯、氯苯、二氯苯和氯仿等，再加入添加剂，添加剂可以选用氯萘、1，8-二碘辛烷等，制得活性层溶液。使用匀胶机在ITO表面旋涂界面修饰层(PEDOT:PSS)，然后将活性层溶液旋涂在界面修饰层表面，旋涂需要在无水无氧的手套箱中，通过控制旋涂的转速调节活性层的厚度，厚度对于器件的性能有很大影响，一般控制活性层厚度为100nm左右。在活性层表面涂覆PDINO之后放在加热台上，以一定的温度加热，然后进行蒸镀电极Al，最后取出做好的电池。
其中IDIC结构如下所示：
Figure BDA0002394398460000061
实施例2：
本实施例中，噻吩并苯并噻二唑二酮SM1的化学结构与实施例1相同，制备方法与实施例相同。
本实施例中，将SM1通过聚合反应得到SM2，SM2的制备过程与实施例1相同。
本实施例中，将该聚合物SM2应用于太阳能电池。太阳能电池的结构和制备方法与实施例1基本相同，所不同的是活性层材料为PM6、Y6与SM2，按照质量比PM6:Y6:SM2为1:1:0.7混合在溶剂中。
对实施例1与实施例2中的太阳能电池的性能参数进行测试，测试结果如下：
Figure BDA0002394398460000062
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种噻吩并苯并噻二唑二酮有机化合物，其结构式如下：
Figure FDA0002394398450000011
其中，R1为C1-C20烷基以及C1-C20的烷氧基中的一种；Ar为以下基团之一：
噻吩基团、噻吩衍生物基团、并二噻吩基团、并二噻吩衍生物基团、并三噻吩基、并三噻吩衍生物基团、苯并二噻吩基团、苯并二噻吩衍生物基团、吡咯并二噻吩基团、吡咯并二噻吩衍生物基团、戊烷并二噻吩基团、戊烷并二噻吩衍生物基团。
2.如权利要求1所述的噻吩并苯并噻二唑二酮有机化合物，其特征是：所述衍生物基团包括如下基团：
Figure FDA0002394398450000012
其中，R2为C1-C20的烷基，C1-C20的烷氧基、羰基、酯基、苯基、取代苯基、噻吩基、或取代噻吩基。
3.如权利要求1、2所述的噻吩并苯并噻二唑二酮有机化合物的制备方法，其特征是：包括如下步骤：
(1)采用2,1,3-苯并噻二唑-4,7-二硼酸频那醇酯A和化合物B通过Suzuki偶联反应，得到中间体C，反应路线如下所示：
Figure FDA0002394398450000013
(2)中间体C与NBS反应，得到如下化合物D：
Figure FDA0002394398450000021
(3)化合物D和化合物E通过Stille偶联反应得到化合物F，反应路线如下所示：
Figure FDA0002394398450000022
(4)化合物F先进行水解反应，提纯后再和NBS(N-溴代丁二酰亚胺)反应得到如下化合物G：
Figure FDA0002394398450000023
(5)化合物G通过Friedel-Crafts反应得到所述的噻吩并苯并噻二唑二酮聚合物。
4.一种聚合物，其特征是：如权利要求1或2所述的有机化合物与含锡单体发生锡溴偶联聚合反应得到。
5.如权利要求4所述的聚合物，其特征是：所述含锡单体包括PDBT、PDBT-2F、PDBT-2Cl。
6.如权利要求4所述的聚合物作为有机光电活性给体材料的应用。
7.一种太阳能电池，包括活性层，所述活性层由活性给体材料与活性受体材料，所述活性给体材料是权利要求4所述的聚合物。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785126A (zh) * 2022-12-01 2023-03-14 中国科学院宁波材料技术与工程研究所 一种共轭有机分子、光活性层材料、三元有机太阳能电池及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU431166A1 (ru) * 1972-03-29 1974-06-05 Ф. С. Михайлицын Способ получения сульфонов или сульфонамидов аминобенз-2,1,3-тиадиазола
CN102159617A (zh) * 2008-09-19 2011-08-17 默克专利股份有限公司 衍生自双(噻吩并环戊烯并)苯并噻二唑的聚合物及其作为有机半导体的用途
WO2012030942A1 (en) * 2010-09-02 2012-03-08 Konarka Technologies, Inc. Photovoltaic cell containing novel photoactive polymer
CN103772656A (zh) * 2012-10-23 2014-05-07 海洋王照明科技股份有限公司 一种含苯并二噻吩-苯并二(苯并噻二唑)共聚物及其制备与应用
CN103833968A (zh) * 2012-11-23 2014-06-04 海洋王照明科技股份有限公司 含苯并[1,2-b:4,5-b’]二噻吩-噻咯并二(苯并噻二唑)的共聚物及其制备方法和应用
CN103848977A (zh) * 2012-11-29 2014-06-11 海洋王照明科技股份有限公司 含二噻吩苯并噻二唑单元的聚合物及其制备方法和太阳能电池器件
CN103965445A (zh) * 2013-01-31 2014-08-06 海洋王照明科技股份有限公司 含二噻吩苯并噻二唑单元的聚合物及其制备方法和太阳能电池器件
CN104017182A (zh) * 2013-02-28 2014-09-03 海洋王照明科技股份有限公司 含苯并噻二唑基的聚合物及其制备方法和应用
CN104725610A (zh) * 2013-12-24 2015-06-24 海洋王照明科技股份有限公司 二噻吩苯并三噻吩基聚合物及其制备方法和应用

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU431166A1 (ru) * 1972-03-29 1974-06-05 Ф. С. Михайлицын Способ получения сульфонов или сульфонамидов аминобенз-2,1,3-тиадиазола
CN102159617A (zh) * 2008-09-19 2011-08-17 默克专利股份有限公司 衍生自双(噻吩并环戊烯并)苯并噻二唑的聚合物及其作为有机半导体的用途
WO2012030942A1 (en) * 2010-09-02 2012-03-08 Konarka Technologies, Inc. Photovoltaic cell containing novel photoactive polymer
CN103249799A (zh) * 2010-09-02 2013-08-14 默克专利股份有限公司 含新型光活性聚合物的光伏电池
CN103772656A (zh) * 2012-10-23 2014-05-07 海洋王照明科技股份有限公司 一种含苯并二噻吩-苯并二(苯并噻二唑)共聚物及其制备与应用
CN103833968A (zh) * 2012-11-23 2014-06-04 海洋王照明科技股份有限公司 含苯并[1,2-b:4,5-b’]二噻吩-噻咯并二(苯并噻二唑)的共聚物及其制备方法和应用
CN103848977A (zh) * 2012-11-29 2014-06-11 海洋王照明科技股份有限公司 含二噻吩苯并噻二唑单元的聚合物及其制备方法和太阳能电池器件
CN103965445A (zh) * 2013-01-31 2014-08-06 海洋王照明科技股份有限公司 含二噻吩苯并噻二唑单元的聚合物及其制备方法和太阳能电池器件
CN105601889A (zh) * 2013-01-31 2016-05-25 王莎莎 含二噻吩苯并噻二唑单元的聚合物的制备方法
CN104017182A (zh) * 2013-02-28 2014-09-03 海洋王照明科技股份有限公司 含苯并噻二唑基的聚合物及其制备方法和应用
CN104725610A (zh) * 2013-12-24 2015-06-24 海洋王照明科技股份有限公司 二噻吩苯并三噻吩基聚合物及其制备方法和应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
RUNFENG CHEN ET AL.: "Heteroatom Bridged Benzothiazolyls for Organic Solar Cells: A Theoretical Study", <THE JOURNAL OF PHYSICAL CHEMISTRY> *
YONG LIU ET AL.: "Donor-Acceptor copolymers based on dithienopyrrolobenzothiadiazole: Synthesis, characterization, and photovoltaic applications", 《EUROPEAN POLYMER JOURNAL》 *
ZHIYONG FU ET AL.: "Density functional study on the effect of a new ladder-type structure with different substituent groups (R ¼ H, CH3, OCH3 and CN) for donor–acceptor copolymers", 《RSC ADV.》 *
邹文武等: "新型给体-受体型聚合物的合成及其在本体异质结聚合物太阳能电池中的应用", 《有机化学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785126A (zh) * 2022-12-01 2023-03-14 中国科学院宁波材料技术与工程研究所 一种共轭有机分子、光活性层材料、三元有机太阳能电池及其制备方法
CN115785126B (zh) * 2022-12-01 2024-04-30 中国科学院宁波材料技术与工程研究所 一种共轭有机分子、光活性层材料、三元有机太阳能电池及其制备方法

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