CN113801301A - 侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物及其制备方法 - Google Patents
侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物及其制备方法。其先通过取代反应链接苝酰亚胺的湾位稠合吡咯环与异靛蓝制备单体M1，然后将其与甲基锡共轭单体M2加热聚合制得所述侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物。将侧链悬挂湾位稠合吡咯环型苝酰亚胺结构单元引入异靛蓝聚合物给体材料，形成一种新的侧链悬挂苝酰亚胺衍生结构单元的聚合物半导体材料。该聚合物具有良好的溶解性、较高的分子量、良好的热稳定性。
Description
技术领域
本发明属于有机合成领域，涉及一种侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物及其制备方法。
背景技术
苝酰亚胺类化合物是有机半导体材料领域中的一种重要小分子受体，异靛蓝类化合物是有机半导体材料领域中的一种重要小分子给体，将有机小分子受体作为侧链单元引入聚合物给体材料形成单组分聚合物活性层是制备聚合物太阳能电池的重要途经。
但目前研究工作主要集中在将垂挂型苝酰亚胺引入侧链，对横挂型苝酰亚胺引入侧链的研究很少。
基于此，本发明设计了将侧链悬挂湾位稠合吡咯环型苝酰亚胺结构单元引入异靛蓝聚合物给体材料，形成一种新的侧链悬挂苝酰亚胺衍生结构单元的聚合物。
发明内容
本发明的目的在于提供一种侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物及其制备方法，相较于其他异靛蓝类聚合物，其创新在于，将苝酰亚胺小分子受体横挂在给体聚合物的侧链当中，形成一种新型的侧链悬挂结构的聚合物。
苝酰亚胺具有大的平面共轭体系，是构建有机小分子受体的典型构筑单元。通常设计形式为将苝酰亚胺结构作为侧链吸电子构筑单元垂直悬挂于主链之上，较纯粹地应用未修饰的苝酰亚胺共轭核。通过修饰分子骨架，调控苝酰亚胺结构单元的聚集态与物化性质，拓展了苝酰亚胺结构单元作为侧链受体应用于构建单一聚合物活性层的可能性。因此，研究苝酰亚胺以其它形式悬挂于聚合物的侧链具有积极意义。
本发明将横挂型苝酰亚胺引入聚合物的侧链中制备得聚合物，其拥有良好的化学稳定性、较高的分子量、良好的溶解性等优点。
为实现上述目的，本发明采用如下技术方案：
本发明第一个目的是保护一种侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物，其结构式为：
本发明第二个目的是保护所述侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物的制备方法，其是将单体M1、M2与催化剂三(二亚苄基丙酮)二钯(Pd2(dba)3)和配体三(邻甲基苯基)磷(P(o-tolyl)3)溶于无水有机溶剂中，在惰性气体保护下加热回流聚合，经索式提取进行提纯、真空干燥获得所述聚合物；
其中，单体M1的结构式为：
所述有机溶剂为甲苯。
所述单体M1的制备方法如下：
(1)在无水无氧以及氩气氛围下，将1当量的溴代烷基链取代的异靛蓝化合物A
和2.4当量的湾位稠合吡咯环型苝酰亚胺化合物B
溶于有机溶剂N,N-二甲基甲酰胺中，以3当量碳酸钾为催化剂，80℃搅拌反应，经乙酸乙酯萃取后，以二氯甲烷比石油醚体积比为7比1为洗脱剂进行硅胶层析柱提纯得到单体M1。
所述聚合物制备方法如下：
(1)在无水无氧以及氩气氛围下，将1当量单体M1
和1当量单体M2
溶于有机溶剂甲苯中，在0.2％当量的催化剂三(二亚苄基丙酮)二钯(Pd2(dba)3)，0.8％当量的配体三(邻甲基苯基)磷(P(o-tolyl)3)作用下于65℃反应5小时，依次经甲醇、石油醚、氯仿索式提取，真空干燥得到所述聚合物。
本发明的显著优点
(1)本发明所采用的原料相对廉价，合成路径不复杂；
(2)本发明所合成的聚合物在氯仿、四氢呋喃、氯苯等常用有机溶剂中具有很好的溶解性，容易通过滴涂或旋涂的方式形成薄膜，并具有较好吸光范围和良好的化学稳定性。
(3)本发明所合成的聚合物具有出色的热稳定性能，可应用于聚合物太阳能电池等器件中。
附图说明：
图1为本实例合成步骤；
图2为单体M1的核磁共振氢谱；
图3为聚合物的核磁共振氢谱；
图4为聚合物的热重分析曲线；
图5为聚合物的凝胶渗透色谱；
图6为聚合物和单体M1的薄膜紫外可见吸收光谱；
图7为聚合物的循环伏安图。
具体实施方式：
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1溴代烷基链取代的异靛蓝化合物A制备
按文献《Brynn P.Charron，Michael U.Ocheje,Mariia Selivanova,et al，Electronic properties of isoindigo-based conjugated polymers bearing urea-containing and linear alkyl side chains，Journal of Materials Chemistry C.,2018，6，12070》制备溴代烷基链取代的异靛蓝化合物A，其结构式为：
实施例2湾位稠合吡咯环型苝酰亚胺化合物B
按文献《Fei You，Xingbao Zhou，Hongyan Huang，N-Annulated perylenediimide derivatives as non-fullerene acceptors for solution-processed solarcells with an open-circuit voltage of up to 1.14 V，New Journal of Chemistry,42.》制备湾位稠合吡咯环型苝酰亚胺化合物B，其结构式为：
实施例3单体M1的制备：
在氩气氛下，将实例2制得的化合物B(1.69mmol，1.20g)与实例1制得的化合物A(0.70mmol，0.52g)和碳酸钾(2.1mmol，0.29g)溶解在装有N,N-二甲基甲酰胺(30mL)的100mL耐压管中，在80℃搅拌反应，对反应进行TLC跟踪。36小时后反应结束，加入冷水。乙酸乙酯进行萃取，所得有机相用水洗涤，收集有机相，用无水硫酸镁干燥后所得滤液减压除去溶剂得粗产物。将粗产物用硅胶层析柱提纯(洗脱剂为体积比为7:1的二氯甲烷：石油醚)，并用甲醇重结晶并真空干燥后得到红棕色固体，即为单体M1，产量为1.40g，产率为50％，TLC比移值Rf＝0.48(展开剂为二氯甲烷：石油醚＝7:1，体积比)。1HNMR(400MHz,CDCl3)δ8.99(s,8H),8.87(s,2H),8.82(s,4H),6.99(s,2H),6.78(s,2H),5.30(s,4H),4.87(s,4H),3.64(s,4H),2.30(s,8H),2.20(s,4H),1.92(s,8H),1.62(s,4H),1.30(s,58H),0.81(s,24H)。其结构为：
实例4单体M2的制备：
按文献《Joonhyeong Choi,Ki-Hyun Kim,Hojeong Yu,Importance of ElectronTransport Ability in Naphthalene Diimide-Based Polymer Acceptors for High-Performance,Additive-Free,All-Polymer Solar Cells，Chemistry of Materials 201527(15),5230-5237》制备单体M2，其结构为：
实施例5侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物的制备：
在氩气氛下，将单体M1(0.1mmol，200.8mg)和单体M2(0.1mmol，49.2mg)加入100mLSchleck反应管中，再加入7mL无水甲苯。鼓泡除氧30分钟后，加入催化剂三(二亚苄基丙酮)二钯(Pd2(dba)3)(0.002mmol，1.9mg)，配体三(邻甲基苯基)磷(P(o-tolyl)3)(0.008mmol，2.5mg)，封管于65℃反应5小时。待反应冷却至室温，用甲醇进行沉淀得粗产物，依次用甲醇、石油醚与氯仿进行索氏提取，收集氯仿提取部分。减压除去溶剂后，用甲醇进行二次沉淀，再过滤并真空干燥得到黑色固体即为聚合物，产量为197mg，产率为98％。1H NMR(400MHz,CDCl3)δ8.86(s,6H),8.61(s,3H),7.52(s,1H),7.00(s,3H),6.90(s,1H),6.62(s,2H),6.30(s,1H),5.23(s,2H),4.84(s,1H)。其结构为：
聚合物的热重分析、凝胶渗透色谱、紫外吸收光谱、循环伏安图
图4给出了聚合物物的热重分析曲线，曲线上损失5％重量百分比时所对应的温度(Td)视为材料的热分解温度。由图4可知，聚合物的热分解温度(Td)为375℃，表明其具有出色的热稳定性能。图5给出了聚合物的凝胶渗透色谱GPC曲线，测得的数均分子量为20866，重均分子量为51234。图6给出了聚合物和单体M1的薄膜紫外可见吸收光谱，由图6可知聚合物薄膜的起始吸收(λonset film)为776nm，聚合物是由单体M1聚合而来，单体M1是两共轭结构单元通过非共轭烷基链桥连起来的。聚合物的吸收分为两部分：一是作为共聚单体骨架的异靛蓝单元；二是苝二酰亚胺侧链单元。当共轭单元联噻吩引入到共轭分子链，使共轭分子链的有效共轭长度得到明显提升，分子链内的电荷转移作用明显，薄膜状态下的聚合物的起始吸收波长(λonset film)比相同状态下M1的起始吸收波长增大约200nm，这扩展了聚合物对可见光的吸收范围，有助于对光的利用率提高。图7给出了聚合物的循环伏安图，表征聚合物的电化学性质，循环伏安法测试在PGSTAT302N型电化学工作站上进行。三电极体系：工作电极即铂电极，辅助电极为铂丝电极，参比电极为Ag/AgCl电极。其电解质为0.1M四丁基六氟磷酸铵溶液(溶剂为无水乙腈)。氮气气氛下，扫描速度为100mV/s，测试样品前后以二茂铁作为外标，测试时将聚合物溶解后滴涂在铂盘电极上成膜后进行电化学测试。
Claims (10)
1.一种侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物，其特征在于，其结构为：
2.一种如权利要求1所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物的制备方法，其特征在于，将单体M1、M2与催化剂溶于无水有机溶剂中，在惰性气体下加热回流进行聚合后，经提纯、高温真空干燥获得所述聚合物；其中，单体M1的结构式为：
单体M2的结构为：
3.根据权利要求2所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物的制备方法，其特征在于，包括如下步骤：
(1)将溴代烷基链取代的异靛蓝化合物A与湾位稠合吡咯环型苝酰亚胺化合物B在有机溶剂中发生取代反应，得到单体M1；
(2)单体M1与甲基锡共轭单体M2在催化剂和配体的作用下在无水有机溶剂中发生聚合反应，经索式提取得到所述聚合物。
4.根据权利要求3所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺的异靛蓝聚合物的制备方法，其特征在于，步骤(1)中所述溴代烷基链取代的异靛蓝化合物A的结构式为：
5.根据权利要求3所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺异靛蓝聚合物的制备方法，其特征在于，步骤(1)中所述湾位稠合吡咯环型苝酰亚胺化合物B的结构式为：
6.根据权利要求3所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺异靛蓝聚合物的制备方法，其特征在于，步骤(1)的具体方法为：在无水无氧以及氩气氛围下，将1当量的溴代烷基链取代的异靛蓝化合物A和2.4当量的湾位稠合吡咯环型苝酰亚胺化合物B以3当量碳酸钾为催化剂，以N,N-二甲基甲酰胺为反应介质，进行反应；萃取，进行硅胶层析柱提纯得到单体M1。
7.根据权利要求6所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺异靛蓝聚合物的制备方法，其特征在于，萃取剂为乙酸乙酯进行萃取；硅胶层析柱提纯的洗脱剂为以二氯甲烷比石油醚体积比为7比1的洗脱剂。
8.根据权利要求6所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺异靛蓝聚合物的制备方法，其特征在于，具体反应温度为80℃，反应时间为36小时。
9.根据权利要求3所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺异靛蓝聚合物的制备方法，其特征在于，步骤(2)的具体方法为：在无水无氧以及氩气氛围下，将1当量的单体M1和1当量的5,5'-双(三甲基锡烷基)-2,2'-联噻吩单体M2溶解于无水甲苯中，在65℃，2％当量的催化剂三(二亚苄基丙酮)二钯Pd2(dba)3和8％当量的配体三(邻甲基苯基)磷P(o-tolyl)3的作用下反应，依次经甲醇、石油醚和氯仿索氏提取，真空干燥得到聚合物。
10.根据权利要求9所述的侧链悬挂湾位稠合吡咯环型苝酰亚胺异靛蓝聚合物的制备方法，其特征在于，反应时间为5小时。
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