CN112062938B - 基于吲哚酮与萘二酰亚胺单元的共轭聚合物及其制备方法 - Google Patents
基于吲哚酮与萘二酰亚胺单元的共轭聚合物及其制备方法 Download PDFInfo
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Abstract
本发明涉及基于吲哚酮与萘二酰亚胺单元的共轭聚合物及其制备方法。所述共轭聚合物的结构式如下：
其中，R1，R2,R3为支化烷基链，n≥1。本发明还涉及基于吲哚酮与萘二酰亚胺单元的共轭聚合物的制备方法。本发明中的基于吲哚酮与萘二酰亚胺单元的共轭聚合物具有在可见‑近红外区宽而强的吸收。萘二酰亚胺以及吲哚酮上的侧链烷基为本发明提供良好的溶解度因此该材料可溶液加工。本发明中基于吲哚酮与萘二酰亚胺单元的共轭聚合物通过碳氢活化聚合而成。该方法合成步骤简单、且无金属副产物，能获得较高的分子量、较少的结构缺陷的聚合物。本发明所涉及聚合方法符合环保、经济的绿色化学原则。
Description
技术领域
本发明涉及一种在可见光近红外区有强吸收的有机半导体受体聚合物及其制备方法，属于有机太阳能电池受体材料领域。
背景技术
有机太阳能电池因其成本低，可溶液加工，可制作柔性器件等特点，在近年来，受到大家的广泛关注。有机太阳能电池的主要材料是有机共轭聚合物，其聚合方法大都采用卤化单体与有机金属单体进行碳-碳键偶联，比如Stille偶联，Suzuki偶联等。这种合成策略可以合成大多数的共轭聚合物，但同时这些反应存在问题是必须使用有机金属化合物(硼酸,硼酸酯，丁基锂或有机锡试剂等),而这些有机金属化合物的使用需要增加额外的合成步骤和纯化步骤.通常反应产生的副产物具有一定的毒性,增加其制备和提纯难度，同时对环境产生极大的危害。
近年来，通过卤化单体与具有活泼氢的单体进行直接活化和诱导碳-氢键形成碳-碳键来合成聚合物的合成策略，引起大家的重视。该方法不需要预活化sp2碳-氢键，即不必合成有机金属单体。不仅简化了合成步骤，且不涉及有机金属化合物的使用，同时反应无金属副产物，减少聚合物结构的缺陷。相比于Stille偶联，Suzuki偶联等聚合方法，采用碳氢活化进行聚合，更加符合绿色化学、更具有原子经济性。但碳氢活化偶联一般较多的应用于小分子化合物，在合成聚合物方面应用报道较少。
发明内容
本发明的目的是提供一种通过碳氢活化偶联反应合成的n-型共轭聚合物受体材料，得到两种基于吲哚酮与萘二酰亚胺单元的共轭聚合物。该聚合物采用直接碳氢活化合成，具有原料简单易得，合成简便，制备过程绿色环保，适用大规模生产。本发明的聚合物可溶液处理，在可见光区域具有宽而强的光吸收。在有机太阳能电池受体材料方面有很大的应用潜力。
本发明的目的是通过以下的技术方案实现的：
第一方面，本发明涉及基于吲哚酮与萘二酰亚胺单元的共轭聚合物，所述共轭聚合物的结构式如式(Ⅰ)所示：
第二方面，本发明涉及基于吲哚酮与萘二酰亚胺单元的共轭聚合物的方法，包括如下步骤：
具体包括如下步骤：
按摩尔量份数，将1份单体M1，1份单体M2，0.01-0.02份催化剂Pd2(dba)3，3份K2CO3，1份新戊酸，溶于无水卤代有机溶剂中；整个体系在无氧气氛下，加热回流；聚合后，经过索氏提取进行提纯，真空干燥获得深蓝色共轭聚合物P。
所述单体M1的结构式如式(Ⅱ)所示：
所述单体M2的结构式如式(Ⅳ)所示：
所述单体M2的制备方法参考文献《冯士振.基于萘二酰亚胺单元的受体材料的设计合成及其光伏性能的研究[D].华南理工大学,2018.》。
所述加热回流具体为：80℃～120℃中反应较短时间，一般为2～3小时；所述索氏提取依次采用的溶剂为甲醇、石油醚和氯仿。
所述单体M1具体制备步骤为：
a、按摩尔量份数，将1.1份含溴吲哚酮物质A与1份噻吩甲醛化合物B加到有机溶剂，以80℃回流反应20多小时；反应结束后，经萃取提纯干燥后得到中间化合物C；
所述含溴吲哚酮物质A具有如下结构：
所述噻吩甲醛化合物B具有如下结构：
所述中间化合物C具有如下结构：
b、按摩尔量份数，将步骤a所得中间化合物C1份溶于在有机溶剂中，与1.1份三丁基锡噻吩、0.02-0.04份的催化剂、0.06-0.08份的配体以100-120℃反应24小时，得到了单体M1前置体D；
所述前置体D具有如下结构：
c、按摩尔量份数，在有机溶剂中，加入1份步骤b所得中间化合物D与5份溴化烃，以及10份碳酸钾，以100-120℃反应24小时，经硅胶柱提纯后得到单体M1。
所述步骤a有机溶剂为甲醇；所述步骤b有机溶剂为N,N二甲基甲酰胺，催化剂为三(二亚苄基丙酮)二钯、配体为三邻甲苯基膦；所述步骤c有机溶剂为N,N二甲基甲酰胺。
本发明的显著优点
(1)本发明合成的N型NDI聚合物所采取的聚合方法是碳氢活化，该方法不需要使用有机金属单体、无金属副产物，是一种绿色环保且具有原子经济性的聚合方法。
(2)本发明所采用的原料均为普通的化工原料，容易获得，且合成工艺简单成熟，其价格低廉，合成成本低
(3)本发明的半导体聚合物，其主链具有刚性平面的大π共轭结构，侧链为可增加聚合物柔性的烷基结构，使聚合物具有可溶液加工处理，方便其作为太阳能电池器件的应用。
(4)本发明的聚合物具有较大的光吸收范围，良好的化学稳定性，低的未占有轨道能级。适合作为太阳能电池器件的受体材料。
附图说明
图1为本发明实施例1中聚合物P的合成路线图
图2为本发明实施例1中的单体M1-1核磁共振氢谱。
图3为本发明实施例1中的单体M1-2核磁共振氢谱。
图4为本发明实施例1中的聚合物P1核磁共振氢谱。
图5为本发明实施例1中的聚合物P2核磁共振氢谱。
图6为本发明实施例2中聚合物P1紫外光谱。
图7为本发明实施例3中聚合物P2紫外光谱。
图8为本发明实施例2中聚合物P1的CV曲线图。
图9为本发明实施例3中聚合物P2的CV曲线图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1、基于吲哚酮与萘二酰亚胺单元的共轭聚合物共轭聚合物的制备
本实施例提供了2种可溶性的基于吲哚酮与萘二酰亚胺单元的共轭聚合物，其结构式如表1所示(其中，n≥1)，其合成路线参见图1。
1.1、单体M1的制备
P1、P2聚合物的第一种单体M1(M1-1、M1-2)的合成路线大致相同，其具体包括以下步骤：
(a)中间化合物C的合成
中间体化合物C的结构式为
其详细制备方法为：在氮气的保护下，将6-溴-2-吲哚酮(20mmol),2-噻吩甲醛(22mmol)投入到双口烧瓶中，再加入一定量的甲醇，其反应物形成悬浮液。再量取5ml的哌啶加入到混合液中，于一定温度(50℃-90°℃中的任意值)反应一定时间(10-24小时中的任意值)。反应结束后，冷却至室温，将生成的混合物过滤，依次用水、甲醇、乙酸乙酯将产物清洗，真空烘干后的中间化合物C(产率为76.8％)。
(b)单体M1前置体D的合成
单体M1前置体D的结构式为
其详细制备方法为：在氮气保护下，将中间化合物C(3.26mmol)、三丁基锡噻吩(3.56mmol)以及有机溶剂DMF加入到耐压管中，经过一段时间的鼓泡除氧，再加入二价钯催化剂(0.065mmol)以及磷配体(0.08mmol)。反应24小时后，停止反应待冷却至室温，加入稀盐酸搅拌，用布氏漏斗过滤，依次用水、石油醚清洗，用甲醇、二氯甲烷重结晶，过滤干燥得棕色固体单体M1前置体D(产率为46％)。
(c)单体M1的合成
单体M1的结构式为
其制备方法为：将单体M1前置体D(1.5mmol)、碳酸钾(15mmol)、溴化烃(7.5mmol)以及一定量的有机溶剂DMF投入到干燥的双口瓶。在氮气氛下，加热到100℃-120℃的某个温度，反应24小时。停止反应，待其冷却到室温，将反应产物倒入水中。用二氯甲烷萃取，依次用清水、饱和食盐水洗涤，用无水硫酸镁干燥后，将反应产物投入到层析柱中进行分离提纯得到粗产物。然后用甲醇重结晶得到单体M1。
1.2、单体M2的制备
P1、P2聚合物的第二种单体M2(M2-1、M2-2)的合成方法大致相同，这里主要介绍M2-1的制备其具体包括以下步骤：
(a)化合物E的合成
化合物E的结构为
其制备方法见文献《冯士振.基于萘二酰亚胺单元的受体材料的设计合成及其光伏性能的研究[D].华南理工大学,2018.》。
(b)单体M2-1的合成
单体M2-1的结构为
其制备方法见文献《冯士振.基于萘二酰亚胺单元的受体材料的设计合成及其光伏性能的研究[D].华南理工大学,2018.。
1.3、聚合物P的合成
对聚合物的聚合条件进行多次优化，首先是对催化剂的选择，采用多种钯催化剂进行试验，比如[1,1'-双(二苯基膦基)二茂铁]二氯化钯，二溴化钯等。对投料配比也进行多次试验，最终优化后聚合条件如下。
在氮气保护下，将单体M1(0.25mmol)、M2(0.25mmol)、新戊酸(0.25mmol)碳酸钾(0.75mmol)以及0.6mL氯苯投入到耐压管中，进行鼓泡除氧，最后加入催化剂三(二亚苄基丙酮)二钯(0.0025-0.0030mmol)，于一定温度(可为80℃～120℃中的任意值)反应一定时间(可为2～5小时中的任意值)，将反应液冷却到室温，加入一定量甲醇沉淀，过滤出固体，依次用甲醇、石油醚、氯仿索氏提取，收集氯仿溶液，旋干后再用甲醇沉淀得有金属光泽的聚合物。P1和P2产率均为90％以上。
实施例2、聚合物P1的紫外吸收光谱和电化学性质
2.1、聚合物P1的紫外吸收光谱
图6给出了聚合物P1在氯仿和薄膜时的紫外吸收光谱，可看到聚合物有两个吸收峰，在薄膜中，带侧链的NDI在350nm-550nm具有强吸收，噻吩-2-吲哚酮-噻吩在600nm-780nm有较强的吸收，总体而言，其紫外可见光吸收范围广。薄膜的起始吸收(λonsetfilm)为842nm，根据公式Egfilm＝1240/λonsetfilmeV计算可得Egfilm＝1.47eV，说明该聚合物是一个窄带隙聚合物。
2.2、聚合物P1的电化学性质
以铂片为工作电极，铂丝为对电极，饱和甘汞电极为参比电极，对聚合物的电化学性能进行了测试。在无水乙腈溶剂中，以浓度为0.1mol/L的四丁基六氟磷酸铵为电解质，扫描速度为100mV/s，在铂片上对聚合物进行了测试，并给出了聚合物的电化学曲线，见图8。我们根据下面的公式导出了聚合物的HOMO和LUMO以及能隙。EHOMO＝﹣(Eox onset+4.36)eV，ELUMO＝﹣(Ere onset+4.36)eV，Eg＝ELUMO－EHOMO，Eox onse是起始氧化电势，Ere onset是起始还原电势。
从图中可知道，聚合物的起始还原电位和氧化电位分别为-0.57V和1.27V。根据上述公式计算出，聚合物的HOMO能级和LUMO能级分别为-5.63eV和-3.79eV。从其能级的角度看可以成为太阳能受体材料。
实施例3、聚合物P2的紫外吸收光谱和电化学性质
3.1、聚合物P2的紫外吸收光谱
图7给出了聚合物P2在氯仿和薄膜时的紫外吸收光谱，可看到聚合物的两个吸收峰其吸收强度差不多。因此聚合物P2的紫外可见光吸收范围广而且吸收强度高。薄膜的起始吸收(λonsetfilm)为845nm，根据公式Egfilm＝1240/λonsetfilmeV计算可得Egfilm＝1.47eV。
3.2、聚合物P2的电化学性质
以铂片为工作电极，铂丝为对电极，饱和甘汞电极为参比电极，对聚合物的电化学性能进行了测试。在无水乙腈溶剂中，以浓度为0.1mol/L的四丁基六氟磷酸铵为电解质，扫描速度为100mV/s，在铂片上对聚合物进行了测试，并给出了聚合物的电化学曲线，见图9。我们根据下面的公式导出了聚合物的HOMO和LUMO以及能隙。EHOMO＝﹣(Eox onset+4.36)eV，ELUMO＝﹣(Ere onset+4.36)eV，Eg＝ELUMO－EHOMO，Eox onse是起始氧化电势，Ere onset是起始还原电势。
从图中可知道，聚合物的起始还原电位和氧化电位分别为-0.59V和1.19V。根据上述公式计算出，聚合物的HOMO能级和LUMO能级分别为-5.55eV和-3.77eV。从其能级的角度看可以成为太阳能受体材料。
Claims (5)
1.基于吲哚酮与萘二酰亚胺单元的共轭聚合物，其特征在于，所述共轭聚合物的结构式如式(Ⅰ)所示：
其中，R1、R2、R3为支化烷基链，n≥1。
2.一种制备如权利要求1所述的基于吲哚酮与萘二酰亚胺单元的共轭聚合物的方法，其特征在于：包括如下步骤：
按摩尔量份数，将1份单体M1，1份单体M2，0.01-0.02份催化剂Pd2(dba)3，3份K2CO3，1份新戊酸，溶于无水卤代有机溶剂中；整个体系在无氧气氛下，加热回流；聚合后，经过索氏提取进行提纯，真空干燥获得深蓝色共轭聚合物P；所述单体M1的结构式如式(Ⅱ)所示：
所述单体M2的结构式如式(Ⅳ)所示：
3.根据权利要求2所述的基于吲哚酮与萘二酰亚胺单元的共轭聚合物的制备方法，其特征在于，所述单体M1具体制备步骤为：
a、按摩尔量份数，将1.1份含溴吲哚酮物质A与1份噻吩甲醛化合物B加到有机溶剂，以80°C回流反应20多小时；反应结束后，经萃取提纯干燥后得到中间化合物C；
所述含溴吲哚酮物质A具有如下结构：
(A)
所述噻吩甲醛化合物B具有如下结构：
(B)
所述中间化合物C具有如下结构：
(C)
b、按摩尔量份数，将步骤a所得中间化合物C 1份溶于在有机溶剂中，与1.1份三丁基锡噻吩、0.02-0.04份的催化剂、0.06-0.08份的配体以100-120℃反应24小时，得到了单体M1前置体D；
所述前置体D具有如下结构：
(D)
c、按摩尔量份数，在有机溶剂中，加入1份步骤b所得中间化合物D与5份溴化烃，以及10份碳酸钾，以100-120℃反应24小时，经硅胶柱提纯后得到单体M1。
4.根据权利要求3所述的基于吲哚酮与萘二酰亚胺单元的共轭聚合物的制备方法，其特征在于，所述步骤a有机溶剂为甲醇；所述步骤b有机溶剂为N,N二甲基甲酰胺，催化剂为三(二亚苄基丙酮)二钯、配体为三邻甲苯基膦；所述步骤c有机溶剂为N,N二甲基甲酰胺。
5.根据权利要求2所述的基于吲哚酮与萘二酰亚胺单元的共轭聚合物的制备方法，其特征在于，所述加热回流具体为：80℃～120℃中反应较短时间，具体为2～3小时；所述索氏提取依次采用的溶剂为甲醇、石油醚和氯仿。
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