CN108148182B - 一种基于环酰亚胺稠合苯并噻二唑的共轭化合物及其制备方法和应用 - Google Patents

一种基于环酰亚胺稠合苯并噻二唑的共轭化合物及其制备方法和应用 Download PDF

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CN108148182B
CN108148182B CN201711278036.6A CN201711278036A CN108148182B CN 108148182 B CN108148182 B CN 108148182B CN 201711278036 A CN201711278036 A CN 201711278036A CN 108148182 B CN108148182 B CN 108148182B
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兰柳元
麦裕良
文武
高敏
廖兵
李岱远
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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Abstract

本发明公开了一种基于环酰亚胺稠合苯并噻二唑的共轭化合物及其制备方法和应用。这种基于环酰亚胺稠合苯并噻二唑的共轭化合物，其结构式如式(Ι)所示：

Description

一种基于环酰亚胺稠合苯并噻二唑的共轭化合物及其制备方 法和应用
技术领域
本发明涉及一种基于环酰亚胺稠合苯并噻二唑的共轭化合物及其制备方法和应用。
背景技术
太阳能是一种绿色可再生能源，有机太阳能电池具有低成本、轻重量、半透明、可溶液加工成大面积的柔性薄膜器件等优点，因此在学术界和商业界受到广泛的关注。近年来，通过对活性层材料和器件结构及制备条件的不断优化，有机太阳能电池发展迅速，取得了显著的成果，目前基于聚合物给体或小分子给体与富勒烯受体共混制备的太阳能电池的光电转化效率已突破11％，市场化前景十分光明。
为了获得高效的有机太阳能电池器件，材料是最重要的因素之一。相比于给体材料的迅速发展，受体材料则发展缓慢。在受体材料方面，以PC61BM和PC71BM为代表的富勒烯衍生物占据着主导地位。这是因为PCBM具有大的电子亲和力、高电子迁移率、并且能够与共轭聚合物给体材料混合形成纳米尺寸的相分离结构等。然而以PCBM为代表的富勒烯衍生物自身也存在着难于克服的缺点，比如可见光区吸收弱，能级难于调控，导致开路电压较低，限制了光电转换效率的进一步提高。相比之下，非富勒烯类有机小分子受体材料的结构易于修饰，能级容易微调，使其与给体材料的能级能够很好地相互匹配，从而获得高的开路电压。
近几年，人们为了替换有机太阳能电池中的富勒烯受体，合成了一系列的新型小分子非富勒烯受体材料，当其与不同的给体材料共混制备太阳能电池时，表现出了良好的光电性能。但是，目前有机小分子非富勒烯受体材料开发不足，局限于苝二酰亚胺、萘二酰亚胺以及平面型多元稠环类材料。因此，为了实现有机太阳能电池高效的光电转换，加速其商业化进程，从活性层材料的角度上考虑，合成更多的新型受体材料就显得十分重要。
发明内容
本发明的目的在于提供一种基于环酰亚胺稠合苯并噻二唑的共轭化合物及其制备方法和应用。
本发明所采取的技术方案是：
一种基于环酰亚胺稠合苯并噻二唑的共轭化合物，其结构式如式(Ι)所示：
Figure BDA0001496977370000021
式(Ι)中，R1、R2和R3独立地为氢原子或C1～C24的烷基链，所述C1～C24烷基链中的一个或多个碳原子可被氧原子取代；
A为拉电子基团；
Ar为芳香基团；
X为O、S或Se；
n为0～6的自然数，m为0～2的自然数。
优选的，拉电子基团A为以下结构中的任意一种：
Figure BDA0001496977370000022
其中，R4为氢原子或C1～C24的烷基链，所述C1～C24烷基链中的一个或多个碳原子可被氧原子取代。
优选的，Ar为以下结构中的任意一种：
Figure BDA0001496977370000031
其中，R5为氢原子或C1～C24的烷基链，所述C1～C24烷基链中的一个或多个碳原子可被氧原子取代。
这种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，是在惰性气体氛围中，将以环酰亚胺稠合苯并噻二唑为核的双溴代化合物与拉电子基团A的单硼酸酯化合物混合于碱性溶剂中，在催化剂的作用下进行反应，所得的产物经萃取，提纯，得到式(Ι)所示结构的化合物。
制备方法中，以环酰亚胺稠合苯并噻二唑为核的双溴代化合物与拉电子基团A的单硼酸酯化合物的摩尔比为1：(2～8)；催化剂与以环酰亚胺稠合苯并噻二唑为核的双溴代化合物的摩尔比为1：(10～20)。
制备方法中，催化剂为四(三苯基膦)钯催化剂。
制备方法中，碱性溶剂为四氢呋喃和碳酸钾水溶液的混合物，碳酸钾水溶液的浓度为1mol/L～2mol/L，碳酸钾与以环酰亚胺稠合苯并噻二唑为核的双溴代化合物的摩尔比为1：(0.01～0.02)，四氢呋喃的用量与以环酰亚胺稠合苯并噻二唑为核的双溴代化合物的用量比为(200～300)mL：1g。
制备方法中，反应的温度为60℃～80℃，反应的时间为24h～48h。
这种基于环酰亚胺稠合苯并噻二唑的共轭化合物在制备有机太阳能电池中电子受体或电子给体材料的应用。
本发明的有益效果是：
本发明公开的基于环酰亚胺稠合苯并噻二唑为核的共轭化合物结构新颖，制备方法简单，其热稳定性很好，太阳光子吸收能力强，电子能级合适，适合用于有机太阳能电池中的电子受体或电子给体材料。
具体如下：
1、合成的基于环酰亚胺稠合苯并噻二唑为核的共轭化合物结构新颖，具有独创性；
2、合成的基于环酰亚胺稠合苯并噻二唑为核的共轭化合物溶于氯仿、四氢呋喃和氯苯等有机溶剂，可采用溶液法加工；
3、合成的基于环酰亚胺稠合苯并噻二唑为核的共轭化合物的热稳定性很好，太阳光子吸收能力强，电子能级合适，适合用于有机太阳能电池中的电子受体或电子给体材料，尤其是在有机太阳能电池中能够获得较高的开路电压。
附图说明
图1是实施例所制备的共轭化合物BIBTNI在四氢呋喃溶液和薄膜中的吸收光谱图；
图2是实施例所制备的共轭化合物BIBTNI的热失重曲线图；
图3是实施例所制备的共轭化合物BIBTNI的有机太阳能电池的J-V曲线图。
具体实施方式
一种基于环酰亚胺稠合苯并噻二唑的共轭化合物，是基于环酰亚胺稠合苯并噻二唑为核，齐聚五元芳香杂环和给电子芳香基团为桥接单元，末端为拉电子单元的共轭小分子，其结构式如式(Ι)所示：
Figure BDA0001496977370000041
式(Ι)中，R1、R2和R3独立地为氢原子或C1～C24的烷基链，所述C1～C24烷基链中的一个或多个碳原子可被氧原子取代；
A为拉电子基团；
Ar为芳香基团；
X为O、S或Se；
n为0～6的自然数，m为0～2的自然数。
优选的，拉电子基团A为以下结构中的任意一种：
Figure BDA0001496977370000042
Figure BDA0001496977370000051
其中，R4为氢原子或C1～C24的烷基链，所述C1～C24烷基链中的一个或多个碳原子可被氧原子取代。
优选的，Ar为以下结构中的任意一种：
Figure BDA0001496977370000052
其中，R5为氢原子或C1～C24的烷基链，所述C1～C24烷基链中的一个或多个碳原子可被氧原子取代。
C1～C24的烷基链可以为直链、支链或者环状烷基链。
进一步举例，基于环酰亚胺稠合苯并噻二唑的共轭化合物其结构式为：
Figure BDA0001496977370000053
这种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，是在惰性气体氛围中，将以环酰亚胺稠合苯并噻二唑为核的双溴代化合物与拉电子基团A的单硼酸酯化合物混合于碱性溶剂中，在催化剂的作用下进行反应，所得的产物经萃取，提纯，得到式(Ι)所示结构的化合物。
优选的，制备方法中，以环酰亚胺稠合苯并噻二唑为核的双溴代化合物与拉电子基团A的单硼酸酯化合物的摩尔比为1：(2～8)。
优选的，制备方法中，催化剂与以环酰亚胺稠合苯并噻二唑为核的双溴代化合物的摩尔比为1：(10～20)。
优选的，制备方法中，催化剂为四(三苯基膦)钯催化剂。
优选的，制备方法中，碱性溶剂为四氢呋喃和碳酸钾水溶液的混合物，碳酸钾水溶液的浓度为1mol/L～2mol/L，碳酸钾与以环酰亚胺稠合苯并噻二唑为核的双溴代化合物的摩尔比为1：(0.01～0.02)，四氢呋喃的用量与以环酰亚胺稠合苯并噻二唑为核的双溴代化合物的用量比为(200～300)mL：1g。
优选的，制备方法中，反应的温度为60℃～80℃，反应的时间为24h～48h。
优选的，制备方法中，萃取，提纯具体为采用二氯甲烷进行萃取，有机相浓缩后通过色谱柱提纯。
优选的，制备方法中，惰性气体为氩气或氮气。
制备方法中，以环酰亚胺稠合苯并噻二唑为核的双溴代化合物带有R1，R2，R3和R5取代基。
这种基于环酰亚胺稠合苯并噻二唑的共轭化合物在制备有机太阳能电池材料中的应用。
优选的，这种基于环酰亚胺稠合苯并噻二唑的共轭化合物作为活性层电子受体或电子给体材料在有机太阳能电池中的应用。
以下通过具体的实施例对本发明的内容作进一步详细的说明。
实施例：
一种基于环酰亚胺稠合苯并噻二唑的共轭化合物BIBTNI的合成线路示意如下：
Figure BDA0001496977370000061
在150mL两口圆底烧瓶中分别加入化合物1(0.4g，0.6mmol)，化合物2(0.68g，1.56mmol)，再加入100mL四氢呋喃作溶剂，开启搅拌，加入K2CO3(5.6g，40.5mmol)的水溶液(1.5M)，然后通氩气排气泡30分钟后，加入Pd(PPh3)4(36mg)，开启加热，回流反应过夜。反应完后，冷却至常温，用二氯甲烷萃取，浓缩有机相，用硅胶柱色谱分离提纯，得到红色固体产物BIBTNI(0.5g，产率70％)。
1HNMR(300MHz,CDCl3)：δ＝8.80(d,2H)，δ＝8.67(t,4H)，δ＝8.15(d,2H)，δ＝8.00(d,2H)，δ＝7.83(t,2H)，δ＝7.53(d,2H)，δ＝4.16(d,4H)，δ＝3.71(d,2H)，δ＝1.97(m,3H)，δ＝1.25-1.40(m,24H)，δ＝0.89-0.97(m,18H)。
这种基于环酰亚胺稠合苯并噻二唑为核的共轭化合物BIBTNI的紫外-可见吸收光谱如附图1所示；热失重曲线如附图2所示(5％失重量的热分解温度为430℃)；所制备有机太阳能电池的J-V曲线如图3所示。
有机太阳能电池器件的制备与性能测试
有机太阳能电池采用倒装器件结构，器件结构为ITO/ZnO/活性层/MoO3/Al，导电玻璃ITO作为电子收集电极，ITO玻璃依次用丙酮、洗涤剂、去离子水和异丙醇超声洗涤，然后放入烘箱80℃过夜烘干。在空气中，将电子抽取层材料ZnO旋涂至干净的ITO衬底上，旋涂转速为3000转/秒，紧接着对ITO/ZnO复合衬底进行200℃热退火60min，ZnO薄膜的厚度约为40nm。加热完毕后将ITO/ZnO复合衬底转移至充满氮气保护的手套箱中沉积活性层材料。活性层是以实施例中的共轭化合物BIBTNI作为电子受体材料，共轭聚合物材料P3HT作为电子给体材料，两者按照质量比1.2:1共混溶解在二氯苯溶液中，总质量比为30毫克/毫升，将上述共混溶液通过旋涂方法沉积在ITO/ZnO复合衬底上，紧接着在130℃下热退火10min，活性层薄膜厚度为80-90nm，将ITO/ZnO/活性层基片转移到真空蒸镀腔中，在2×10-4Pa的真空条件下，通过热蒸发的方式沉积10nm的空穴抽取层MoO3和100nm的空穴收集电极金属铝。光伏器件活性层的有效面积为0.16cm2。
器件的能量转换效率(PCE)是在AM1.5G太阳光模拟灯(Newport model 94021A)下测得的。太阳模拟灯的光强通过标准硅太阳电池标定为100mW cm-2。电池器件的电流密度-电压(J-V)曲线是通过Keithley 2400电流-电压源表记录测得的。基于P3HT:BIBTNI的有机太阳能电池器件效率可达1.92％，开路电压高达0.78V，表现出其作为非富勒烯受体材料的良好应用前景，相应的J-V曲线见图3。
本发明用核磁共振表征了基于环酰亚胺稠合苯并噻二唑为核的共轭化合物的化学结构，通过热重分析测试了基于环酰亚胺稠合苯并噻二唑为核的共轭化合物的热稳定性，用紫外可见吸收光谱仪测试了基于环酰亚胺稠合苯并噻二唑为核的共轭化合物的光物理性质，将所合成的共轭化合物制备成光电器件表征了其光电性能。
由于环酰亚胺稠合苯并噻二唑的拉电子能力和平面结构，桥接单元的给电子能力，末端拉电子单元的强拉电子能力，本发明的基于环酰亚胺稠合苯并噻二唑为核的共轭化合物具有较强的光子吸收能力、较高的电荷传输性能以及合适的电子能级，适合于作为电子受体或电子给体材料应用于有机太阳能电池中，是一类具有应用前景的材料。
基于环酰亚胺稠合苯并噻二唑为核的共轭化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基于环酰亚胺稠合苯并噻二唑为核的共轭化合物并成功应用在光电领域。
本发明的实施方式不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的包含范围之内。

Claims (7)

1.一种基于环酰亚胺稠合苯并噻二唑的共轭化合物，其特征在于：其结构式如式(Ι)所示：
Figure FDA0002830761810000011
2.权利要求1所述的一种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，其特征在于：在惰性气体氛围中，将
Figure FDA0002830761810000012
与
Figure FDA0002830761810000013
混合于碱性溶剂中，在催化剂的作用下进行反应，所得的产物经萃取，提纯，得到式(Ι)所示结构的化合物。
3.根据权利要求2所述的一种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，其特征在于：
Figure FDA0002830761810000014
与
Figure FDA0002830761810000015
的摩尔比为1：(2～8)；催化剂与
Figure FDA0002830761810000016
的摩尔比为1：(10～20)。
4.根据权利要求3所述的一种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，其特征在于：催化剂为四(三苯基膦)钯催化剂。
5.根据权利要求2所述的一种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，其特征在于：碱性溶剂为四氢呋喃和碳酸钾水溶液的混合物，碳酸钾水溶液的浓度为1mol/L～2mol/L，碳酸钾与
Figure FDA0002830761810000021
的摩尔比为1：(0.01～0.02)，四氢呋喃的用量与
Figure FDA0002830761810000022
的用量比为(200～300)mL：1g。
6.根据权利要求2所述的一种基于环酰亚胺稠合苯并噻二唑的共轭化合物的制备方法，其特征在于：反应的温度为60℃～80℃，反应的时间为24h～48h。
7.权利要求1所述的一种基于环酰亚胺稠合苯并噻二唑的共轭化合物在制备有机太阳能电池中电子受体或电子给体材料的应用。
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