CN110845707B - 一种吡咯并吡咯单酮并四苯类似物聚合物及其制备方法和应用 - Google Patents

一种吡咯并吡咯单酮并四苯类似物聚合物及其制备方法和应用 Download PDF

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CN110845707B
CN110845707B CN201910512494.4A CN201910512494A CN110845707B CN 110845707 B CN110845707 B CN 110845707B CN 201910512494 A CN201910512494 A CN 201910512494A CN 110845707 B CN110845707 B CN 110845707B
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岳晚
王亚洲
杨欣茹
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Sun Yat Sen University
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Abstract

本发明公开了一种吡咯并吡咯单酮并四苯类似物聚合物，是以吡咯并吡咯单酮氮杂并四苯类似物为模块的共轭聚合物。本发明通过一种简单的方法合成出一种新型吡咯并吡咯单酮并四苯类似物，并且以简单的stille偶联聚合方法合成了三类结构的聚合物，相比于其他并苯结构，合成的并苯类似物聚合物具有较高的产率，与吡咯并吡咯相比具有更大的共轭结构，更加有利于空穴的传输。在有机场效应晶体管(OFET)，在有机太阳能电池(OPV)领域具有潜在的应用前景。

Description

一种吡咯并吡咯单酮并四苯类似物聚合物及其制备方法和 应用
技术领域
本发明涉及有机半导体合成技术领域，更具体地，涉及一种吡咯并吡咯单酮并四苯类似物聚合物及其制备方法和应用。
背景技术
由于吡咯并吡咯二酮衍生物具有较大的平面结构，较低的LUMO能级，具有较高的空气稳定性因此是一类非常重要有机半导体材料。目前对吡咯并吡咯二酮改性主要是酰胺修饰烷基或者双键位置修饰不同共轭基团，对于酰胺键一边修饰烷基链，另外一边关环修饰的聚合物没有报道，且现有的技术存在着产率低、反应步骤复杂等缺点。因此以现有的吡咯并吡咯二酮为原料，进行酰胺键一边修饰烷基链，一边关环修饰，并且制备出聚合物具有十分重要的意义，在有机半导体有着十分重要的应用前景包括有机太阳能电池(OPV)、有机发光二极管(OLED)、有机场效应晶体管(OFET)等应用。
发明内容
本发明的目的在于克服现有技术的上述不足，提供一种新型的、稳定的、溶解性好的吡咯并吡咯单酮并四苯类似物聚合物。
本发明的第二个目的是提供所述吡咯并吡咯单酮并四苯类似物聚合物的制备方法。
本发明的上述目的是通过以下技术方案给予实现的：
一种吡咯并吡咯单酮并四苯类似物聚合物，其化学结构通式如下所示：
Figure BDA0002093946450000011
其中，R’为
Figure BDA0002093946450000012
Figure BDA0002093946450000021
R为16～30个C的支链或者直链烷烃。
本发明的吡咯并吡咯单酮并四苯类似物聚合物具有较好的溶解性能，与吡咯并吡咯酮相比具有更大的共轭结构，更加有利于电子的传输，并且最大吸收波长在可见光领域，在有机场效应晶体管(OFET)、有机太阳能电池(OPV)领域具有潜在的应用前景。
优选地，所述的吡咯并吡咯单酮并四苯类似物聚合物其化学结构通式如式VI、VII或VIII所示：
Figure BDA0002093946450000022
；其中，R为16～30个C的支链或者直链烷烃。
本发明还请求保护所述的吡咯并吡咯单酮并四苯类似物聚合物的制备方法，包括如下步骤：
S1.在氮气保护下，向反应容器中加入3,6-二(2-噻吩基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮和碳酸钾，然后加入溶剂并搅拌，最后加入溴代烷烃进行反应，反应完成后经后处理得到化合物II；
S2.向反应容器中加入化合物II、碳酸钾和3-硝基-4-氟苯氰，在溶剂中进行反应，反应完成后经后处理得到化合物III；
S3.将化合物III溶解到氯仿当中，搅拌，加入N-溴代琥珀酰亚胺，反应，萃取，用硅胶柱进行纯化，得到化合物IV；
S4.向反应容器中加入化合物IV和二水氯化亚锡，在溶剂中进行反应，然后加入NaHCO3后过滤，干燥、除去溶剂并烘干，得到烘干产物；再在氮气保护下，向反应容器中加入上述烘干产物和1,4-二氮杂二环[2.2.2]辛烷，然后加入分子筛以及甲苯，最后加入四氯化钛进行反应，反应完成后经后处理得到化合物V；
S5.将化合物V分别与化合物VI’、VII’或VIII’置于反应器当中，加入催化剂三(二亚苄基丙酮)二钯、配体三(邻甲基)苯基磷，再加入甲苯，反应得到化合物VI、VII或VIII；
所述化合物VI’为
Figure BDA0002093946450000031
化合物VII’为
Figure BDA0002093946450000032
化合物VIII’为
Figure BDA0002093946450000033
其中R为16～30个C的支链或者直链烷烃；例如、C16、C17、C18、C19、C20、C21或C22等。
优选地，步骤S1所述3,6-二(2-噻吩基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮的反应摩尔浓度为0.1～2.0mol/L。
优选地，步骤S1所述反应为50～120℃反应10min～4h。
优选地，步骤S1所述溶剂为N,N-二甲基甲酰胺(DMF)。
优选地，步骤S1所述3,6-二(2-噻吩基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮(I)、溴代烷烃和碳酸钾的摩尔比为1：0.9～2.0：1.0～5.0。
优选地，步骤S2所述化合物II的反应摩尔浓度为0.1～2.0mol/L。
优选地，步骤S2所述化合物II、3-硝基-4-氟苯氰和碳酸钾摩尔比为1：2.3～6.2：2～4.0。
优选地，步骤S2所述反应为50～120℃反应1h～4h。
优选地，步骤S2所述溶剂为N,N-二甲基甲酰胺(DMF)。
优选地，步骤S3所述化合物III的浓度为为0.1～2.0mol/L；
优选地，步骤S3所述化合物III、N-溴代琥珀酰亚胺摩尔比为1:1.5～3.0。
优选地，步骤S3所述反应为-20～50℃下反应5～24h。
优选地，步骤S4所述化合物IV和烘干产物的反应摩尔浓度为0.1～3.0mol/L。
优选地，步骤S4所述化合物IV、二水氯化亚锡、1,4-二氮杂二环[2.2.2]辛烷和四氯化钛的摩尔比为1：6～15：6～15：6～15。
优选地，步骤S5所述化合物V与化合物VI’、VII’或VIII’的摩尔比均为1：1～2。
本发明的吡咯并吡咯单酮并四苯类似物聚合物具有较高的空气稳定性能和较好的溶解性能；与吡咯并吡咯酮相比具有更大的共轭结构，更加有利于电子的传输，并且最大吸收波长在可见光领域，在有机场效应晶体管(OFET)、有机太阳能电池(OPV)领域具有潜在的应用前景。本发明还请求保护所述吡咯并吡咯单酮并四苯类似物聚合物在制备有机半导体材料或有机场效应晶体管或有机太阳能电池材料中的应用。
与现有技术相比，本发明具有以下有益效果：
(1)本发明提供了一种新颖吡咯并吡咯单酮并四苯类似物聚合物，所述聚合物具有较高的空气稳定性能和较好的溶解性能，与吡咯并吡咯酮相比具有更大的共轭结构，更加有利于电子的传输，并且最大吸收波长在可见光领域，在有机场效应晶体管(OFET)、有机太阳能电池(OPV)领域具有潜在的应用前景。
(2)本发明的吡咯并吡咯单酮并四苯类似物聚合物的合成方法简单，易于提纯、成本低，相比于其他并苯结构，合成的并苯类似物具有较高的产率，并且每一步产率都高于20％。
附图说明
图1为本发明吡咯单酮的氮杂并四苯相似物聚合物的制备示意图。
图2为本发明吡咯单酮的氮杂并四苯相似物聚合物的制备化学反应方程式。
图3为实施例1中化合物II的1H NMR谱图。
图4为实施例1中化合物II的13C NMR谱图。
图5为实施例1中化合物III的1H NMR谱图。
图6为实施例1中化合物III的13C NMR谱图。
图7为实施例1中化合物IV的1H NMR谱图。
图8为实施例1中化合物IV的13C NMR谱图。
图9为实施例1中化合物V的1H NMR谱图。
图10为实施例1中化合物V的13C NMR谱图。
图11为实施例1中化合物VI的升温1H NMR。
图12为实施例1中化合VI的CV图。
图13为实施例1中化合物VII的升温1H NMR谱图。
图14为实施例1中化合物VII的CV图。
图15为实施例1中化合物VIII的升温1H NMR谱图。
图16为实施例1中化合物VI、VII、VIII的紫外吸收图。
图17为实施例1中化合物VIII的CV图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，以下实施例所用试剂和材料均为市购。
本发明采用瑞士Bruker公司生产的AVANCE III 400M型液体核磁共振谱仪来检测产物得1H NMR、13C NMR谱图，溶剂为氘代氯仿(CDCl3)及氘代二氯甲烷(CD2Cl2)，四甲基硅烷(TMS)为内标。本实验采用瑞士Bruker生产的solariX质量分析飞行质谱仪(Maldi-TOF)来表征分子量，利用Shimadzu公司的UV-3600型紫外可见分光光度计来测定产物的紫外吸收光谱，采用1×1cm的石英比色皿作为样品池，采用上海辰华仪器有限公司的CHI620E电化学分析仪。
本发明下述具体实施方式中的吡咯并吡咯单酮的氮杂并四苯相似物聚合物制备过程中的化学反应方程式如图2所示。
实施例1
一种吡咯单酮的氮杂并四苯相似物聚合物制备方法，包括如下步骤：
(1)将3.00g 3,6-二(2-噻吩基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮(I)和2.9g叔丁醇钾加入到三口圆底烧瓶中，开始脱气然后充氮气，连续三次，然后加入50mL N,N-二甲基甲酰胺(DMF)，搅拌，然后加入1-溴-2-癸基十四烷C24H49Br 4.17g，在室温下反应4h。将得到溶液先旋蒸，然后通过层析柱纯化，通过减压蒸馏即可得到化合物II，得到化合物的质量为1.57g，产率为32％；图3为化合物II的1H NMR谱图，图4为化合物II的13C NMR，通过核磁共振氢谱可以证明合成的化合物为结构II。
(2)将1.46g化合物(II)、1.52g碳酸钾和0.82g 3-硝基-4-氟苯氰加入到圆底烧瓶中，然后加入40mL N,N二甲甲酰胺，加热温度为80℃，反应24h。最后将析出的固体过滤然后减压蒸馏掉溶剂，通过层析柱进行提纯，通过旋转蒸发仪得到化合物III，产率为50％；图5为化合物III的1H NMR谱图，通过核磁共振氢谱可以证明合成的化合物为结构III；图6为化合物13C NMR，通过该谱图可以证明合成的化合物为结构III。
(3)将0.57g化合物III加入到圆底烧瓶中，然后加入5ml氯仿，在0℃下加0.26gN-溴代琥珀酰亚胺，避光处理，在室温下继续反应24h，加水和二氯甲烷萃取，之后通过减压蒸馏去掉溶剂，通过层析柱得到化合物IV，产率为70％。图7为化合物IV的1H NMR，图8为化合物IV的13C NMR，通过该谱图可以证明合成的化合物为结构IV。
(4)将1.23g化合物IV和2.95g二水氯化亚锡加入到圆底烧瓶中，然后加入10mL乙酸乙酯，反应温度为78℃，反应时间为1h，然后加入浓度为10％NaHCO3，然后过滤，加入乙酸乙酯萃取，用无水硫酸钠干燥，减压蒸馏掉溶剂，烘干。将烘干后得到产物，加入到圆底烧瓶中，用氮气保护，加入1,4-二氮杂二环[2.2.2]辛烷3.72g，然后加入分子筛3A以及20mL甲苯，最后加入1.27mL四氯化钛，反应温度为120℃，冷凝回流24h，将得到的溶液通过层析柱提纯，通过减压蒸馏即可得到产物V，产率为35％；图9为化合物V的1H NMR谱图，通过核磁共振氢谱可以证明合成的化合物为结构V；图10为化合物13C NMR。
(5)将40.65mg化合物V，39.58mg VI’，加入1mg Pd2(dba)3,2mg P-(o-tol)3，通过抽充氮气半个小时，加入1ml甲苯，反应4h，通过索氏提取装置得到化合VI，图11为化合物VI的升温氢谱，图12为化合物VI的CV图，从图中可以得出化合物VI的HOMO＝5.49eV，LUMO＝3.34eV；
所述化合物VI’结构式如下所示：
Figure BDA0002093946450000071
(6)将38.26mg化合物V，53.19VII’，加入1mg Pd2(dba)3,2mg P-(o-tol)3，通过抽充氮气半个小时，加入1ml甲苯，反应48h，通过索氏提取装置得到化合VII，图13为化合物VII的升温氢谱，图14为化合物VII的CV图，从图中可以得出化合物VII的HOMO＝5.85eV，LUMO＝3.82eV；
所述化合物VII’结构式如下所示：
Figure BDA0002093946450000072
(7)将20.56mg化合物V，25.54mg VIII’，加入1mg Pd2(dba)3,2mg P-(o-tol)3，通过抽充氮气半个小时，加入1ml甲苯，反应48h，通过索氏提取装置得到化合物VIII，图15为化合物VIII的升温氢谱，图16为化合物VI、VII、VIII紫外吸收图，从图中可以看到最大吸收波长分别为821nm、812nm、799nm；图17为化合物VIII的CV图，从图中可以得出化合物VIII的HOMO＝5.85eV，LUMO＝3.81eV；
所述化合物VIII’的结构式如下所示：
Figure BDA0002093946450000081

Claims (5)

1.一种吡咯并吡咯单酮并四苯类似物聚合物，其特征在于，其化学结构通式如下所示：
Figure FDA0003666382480000011
其中，R’为
Figure FDA0003666382480000012
Figure FDA0003666382480000013
R为16～30个C的支链或者直链烷烃。
2.根据权利要求1所述的吡咯并吡咯单酮并四苯类似物聚合物，其特征在于，其化学结构通式如式VI、VII或VIII所示：
Figure FDA0003666382480000014
Figure FDA0003666382480000015
其中，R为16～30个C的支链或者直链烷烃。
3.权利要求1或2所述的吡咯并吡咯单酮并四苯类似物聚合物的制备方法，其特征在于，包括如下步骤：
S1.在氮气保护下，向反应容器中加入3,6-二(2-噻吩基)-2,5-二氢吡咯并[3,4-c]吡咯-1,4-二酮和碳酸钾，然后加入溶剂并搅拌，最后加入溴代烷烃进行反应，反应完成后经后处理得到化合物II；
S2.向反应容器中加入化合物II、碳酸钾和3-硝基-4-氟苯氰，在溶剂中进行反应，反应完成后经后处理得到化合物III；
S3.将化合物III溶解到氯仿当中，搅拌，加入N-溴代琥珀酰亚胺，反应，萃取，用硅胶柱进行纯化，得到化合物IV；
S4.向反应容器中加入化合物IV和二水氯化亚锡，在溶剂中进行反应，然后加入NaHCO3后过滤，干燥、除去溶剂并烘干，得到烘干产物；再在氮气保护下，向反应容器中加入上述烘干产物和1,4-二氮杂二环[2.2.2]辛烷，然后加入分子筛以及甲苯，最后加入四氯化钛进行反应，反应完成后经后处理得到化合物V；
S5.将化合物V分别与化合物VI’、VII’或VIII’置于反应器当中，加入催化剂三(二亚苄基丙酮)二钯、配体三(邻甲基)苯基磷，再加入甲苯，反应得到化合物VI、VII或VIII；
所述化合物II为
Figure FDA0003666382480000021
化合物III为
Figure FDA0003666382480000022
化合物IV为
Figure FDA0003666382480000023
化合物V为
Figure FDA0003666382480000031
化合物VI’为
Figure FDA0003666382480000032
化合物VII’为
Figure FDA0003666382480000033
化合物VIII’为
Figure FDA0003666382480000034
其中R为16～30个C的支链或者直链烷烃。
4.根据权利要求3所述的制备方法，其特征在于，所述化合物V与化合物VI’、VII’或VIII’的摩尔比均为1：1～2。
5.权利要求1或2所述吡咯并吡咯单酮并四苯类似物聚合物在制备有机半导体材料或有机场效应晶体管或有机太阳能电池材料中的应用。
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