CN111217991A - 一种d-a型共轭聚合物及其制备方法 - Google Patents

一种d-a型共轭聚合物及其制备方法 Download PDF

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CN111217991A
CN111217991A CN202010161511.7A CN202010161511A CN111217991A CN 111217991 A CN111217991 A CN 111217991A CN 202010161511 A CN202010161511 A CN 202010161511A CN 111217991 A CN111217991 A CN 111217991A
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刘治田
陈逸轩
胡六永
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Wuhan Institute of Technology
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Abstract

本发明公开了一种D‑A型共轭聚合物，其结构式为：

Description

一种D-A型共轭聚合物及其制备方法
技术领域
本发明属于有机聚合物及其合成技术领域，具体涉及一种D-A型共轭聚合物及其制备方法。
背景技术
目前，能源危机已给人们敲响警钟，人们在努力寻找各种可替代的清洁能源，其中清洁且丰富的太阳能成为人们关注的重点。目前基于单晶硅的太阳能电池已经发展非常成熟，但是有机太阳能电池由于其拥有制造面积大、成本低、工艺简单、具有柔性等优点正逐渐引起人们的注意。
现有的D-A型分子在获得增大开路电压以及减小能量损失方面仍然有待改进，同时部分D-A型分子由于结构复杂导致分子平面性较差，使得成膜性较差，不利于制成有机光探测器件；同时电荷载流子迁移率进一步限制了其推广性应用。
发明内容
本发明的主要目的在于针对现有技术存在的不足，提供一种以吡咯并吡咯二酮单元(DPP)和二噻吩并吡咯单元(DTP)组成的D-A型共聚物，该聚合物具有较高的HOMO能级、较窄的带隙、良好的溶解性以及较好的光探测性能，且涉及的制备方法简单，适合推广应用。
为实现上述目的，本发明采用的技术方案为：
一种D-A型共轭聚合物，其结构式为：
Figure BDA0002405953270000011
式中，R为C16-C20的直链或支链烷基；X为苯基、1-萘基或2-萘基；n取值范围为70-200。
上述一种D-A型共轭聚合物的制备方法，包括如下步骤：
1)以噻吩基吡咯并吡咯二酮、溴代烷烃为主要原料，进行一次溴代反应得化合物1；然后将其与N-溴代丁二酰亚胺进行二次溴代反应得化合物2，其结构式见式II；
Figure BDA0002405953270000021
2)以二噻吩并吡咯和三甲基氯化锡为主要原料进行卤代反应得化合物3，其结构式见式III；
Figure BDA0002405953270000022
3)将所得化合物2和化合物3，在保护气氛和催化剂作用下进行聚合反应，即得所述D-A型共轭聚合物(结构式见式I，化合物4)。
上述方案中，所述溴代烷烃的碳原子数为16～20。
上述方案中，步骤1)中所述噻吩基吡咯并吡咯二酮与溴代烷烃的摩尔比为1:(2～2.5)；化合物1与N-溴代丁二酰亚胺的摩尔比为1:(2～2.5)。
上述方案中，步骤1)中所述一次溴代反应温度为130～145℃，时间为12～18h；采用的催化剂优选为碳酸钾，溶剂优选为DMF。
上述方案中，步骤1)中所述二次溴代反应温度为室温，时间为12～18h；采用的溶剂优选为三氯甲烷，且化合物1和N-溴代丁二酰亚胺在避光和冰浴条件下混合。
上述方案中，步骤2)中所述二噻吩并吡咯和三甲基氯化锡的摩尔比为1:(2.5～3)。
上述方案中，步骤2)中所述卤代反应温度为室温，时间为12～18h；其中采用的溶剂优选为四氢呋喃，催化剂优选为正丁基锂，且化合物二噻吩并吡咯与正丁基锂在-70～-78℃下混合。
上述方案中，所述化合物2与化合物3的摩尔比为1:1；采用的催化剂优选为四三苯基膦钯，溶剂优选为甲苯。
上述方案中，步骤3)中所述聚合反应温度为100～110℃，时间为72～96h。
上述方案中，所述二噻吩并吡咯的结构式见式IV，
Figure BDA0002405953270000031
上述方案中，所述二噻吩并吡咯的制备方法包括如下步骤：以3-溴噻吩为主要原料，进行一次偶联反应得到3,3'-二溴-2,2'-联噻吩(化合物5)；然后将其与苯胺进行关环反应得到化合物6也就是二噻吩并吡咯，其结构式见式IV，
上述方案中，所述偶联反应温度为室温，时间为8～12h；采用的催化剂为二异丙基氨基锂和氯化铜，溶剂优选为四氢呋喃，且3-溴噻吩和二异丙基氨基锂以及氯化铜在-70～-78℃下混合。
上述方案中，所述化合物5与苯胺的摩尔比为1:(1～1.5)。
上述方案中，所述关环反应温度为90～110℃，时间为12～18h；采用的催化剂由叔丁醇钠、1,1'-双(二苯基膦)二茂铁和三(二亚苄基丙酮)二钯按(8～10):(4～5):1的摩尔比复合而成，溶剂优选为甲苯。
与现有技术相比，本发明的有益效果为：
本发明在以吡咯并吡咯二酮(DPP)作为强受体单元的基础上进一步引入二噻吩并吡咯(DTP)单元，由于其单元自身具有较强的平面性可以一定程度上增强聚合物的平面，此外二噻吩并吡咯本身具有强给电子性同时进一步在其侧链上引入的苯基等共轭侧链可进一步增强其给电子性，从而使所得聚合物具有较一般D-A型聚合物具有更高的开路电压，进而有效增强其光探测性能，为进一步探索纯有机光电探测器材料的类似体系提供理论基础。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
一种D-A型共轭聚合物，其制备方法包括如下步骤：
1)在250ml两口瓶圆底烧瓶中加入噻吩基吡咯并吡咯二酮(6.01g，20mmol)和碳酸钾(13.82g，100mmol)，溶剂N,N-二甲基甲酰胺(DMF)通过硫酸镁除水1小时后过滤，将过滤后的DMF溶剂(150ml)加入到两口瓶圆底烧瓶中，常温通氮气保护30min后，升温至145℃，随后加入1-溴-2-辛基十二烷(15.9g，44mmol)并保持此温度反应12小时；反应完毕后降温至50℃左右，减压蒸馏除去绝大多数DMF，再用二氯甲烷和水萃取分液两到三次后，用MgSO4干燥并过滤，减压除去溶剂，并通过二氧化硅柱层析法纯化，用淋洗剂(体积比为乙酸乙酯：石油醚＝1:20)洗脱，真空干燥得到深红色固体6.28g(化合物1)，产率36.45％，其反应路线如式1所示：
Figure BDA0002405953270000041
2)在250ml两口烧瓶中加入化合物1(3.45g，4mmol)并降温至0℃避光处理，N-溴代丁二酰亚胺(1.57g，8.8mmol)溶解于三氯甲烷(30ml)中，并用滴液漏斗逐滴加入到两口瓶中，待滴加完毕后在室温下避光反应12小时；通过减压除去溶剂，用二氧化硅柱层析法纯化，用淋洗剂(二氯甲烷：石油醚＝1:4)洗脱，得到纯化产物后用乙醇重结晶1次，用真空干燥箱干燥，得到暗红色固体3.06g(化合物2)，产率75.06％，其反应路线如式2所示：
Figure BDA0002405953270000042
3)在50ml反应管中加入二噻吩并吡咯(0.7661g，3mmol)和溶剂四氢呋喃(10ml)，在-78℃温度下降温10min，用注射器逐滴加入正丁基锂(3ml，2.5mol/L)反应5min后移至室温下继续反应1h，将反应管移至-78℃下降温10min，称取三甲基氯化锡(1.49g，7.5mmol)溶解于四氢呋喃(5ml)中，并用注射器加入到反应管中，移至室温下反应12h，待反应完成后，用去离子水淬灭反应，以二氯甲烷和水萃取，并用无水硫酸镁干燥，活性炭吸附过滤，得到的有机相在减压下除去溶剂，并重结晶2次，得到棕色晶体198mg(化合物3)，产率11.36％，其反应路线如式3所示：
Figure BDA0002405953270000051
4)在10ml反应管中加入化合物2(305.76mg，0.3mmol)和化合物3(174.29mg，0.3mmol)并加入催化剂四三苯基膦钯(6.39mg，6μmol)，通氮气保护，加入甲苯(1ml)，并在避光条件下加热到110℃反应72h；待反应完成后在甲醇中沉降，用漏斗抽滤，最后经过索式抽提纯化得到深蓝色固体308.1mg(化合物4，记为PDPPDTP-P)，产率为89.87％，其反应路线如式4所示：
Figure BDA0002405953270000052
其中，本实施例所述二噻吩并吡咯的制备方法包括如下步骤：
1)在250ml的两口烧瓶中加入3-溴噻吩(12.23g，75mmol)和四氢呋喃(THF)(80ml)，通氮气保护，在0℃下降温10min，用滴液漏斗逐滴加入二异丙基氨基锂(8.034g，75mmol)，保持在0℃下反应2h，将两口烧瓶移至-78℃下降温10min，加入无水氯化铜(20.17g，150mmol)，保持-78℃反应2h后移至室温下反应12h；反应完成后加入去离子水淬灭反应，用二氯甲烷和水萃取，保留有机相，通过二氧化硅柱层析法纯化，用淋洗剂(体积比为二氯甲烷：石油醚＝1:10)洗脱，真空干燥得到淡黄色固体4.8g(化合物5)，产率39.5％，其反应路线如式5所示：
Figure BDA0002405953270000061
2)在100ml两口烧瓶中加入化合物5(1.2962g，4mmol)、苯胺(0.447g，4.8mmol)、叔丁醇钠(0.96g，2mmol)、1,1'-双(二苯基膦)二茂铁(0.264g，0.8mmol)和三(二亚苄基丙酮)二钯(0.112g，0.2mmol)，通氮气保护并且避光处理，再加入溶剂甲苯(10ml)并加热至110℃保温反应12h；待反应完成后用去离子水淬灭反应，用二氯甲烷和水进行萃取，将有机相用无水硫酸镁干燥过滤，经过二氧化硅柱层析法进一步纯化得到淡黄色固体0.0.8198g(化合物6)，产率为80.26％，其反应路线如式6所示：
Figure BDA0002405953270000062
实施例2
一种D-A型共轭聚合物，其制备方法与实施例1大致相同，不同之处在于合成二噻吩并吡咯步骤2)中将苯胺换成1-萘胺；
所得产物记为PDPPDTP-1-N，其结构式为：
Figure BDA0002405953270000063
实施例3
一种D-A型共轭聚合物，其制备方法与实施例1大致相同，不同之处在于合成二噻吩并吡咯步骤2)中将苯胺换成2-萘胺
所得产物记为PDPPDTP-2-N，其结构式为：
Figure BDA0002405953270000071
对比例1
该聚合物记为PDPP3T，其结构式为
Figure BDA0002405953270000072
对比例2
该聚合物记为PDPP2T，其结构式为
Figure BDA0002405953270000073
应用例
将实施例1～3所得产物PDPPDTP-P、PDPPDTP-1-N、PDPPDTP-2-N以及对比例所得聚合物产物分别应用于制备有机光电探测器器件，具体包括如下步骤：首先依次用超纯水、丙酮、异丙醇清洗覆盖有氧化铟锡(ITO)的玻璃基底，然后用氧等离子体处理10分钟，接着将30nm厚的PEDOT:PSS旋涂在基底上并于160℃干燥20分钟；分别将化合物(PDPPDTP-P、PDPPDTP-1-N、PDPPDTP-2-N、PDPP3T、PDPP2T)与PCBM 1:1的质量比溶于1,8-二碘辛烷(DIO)形成混合溶液，将该混合溶液旋涂在基底上面，然后再活性层上旋涂一层氧化锌ZnO(20nm)，得有机光电探测器器件。
本发明实施例1～3所得PDPPDTP-P、PDPPDTP-1-N、PDPPDTP-2-N的成膜性能均优于对比例1和对比例2；且经测试，分别利用本发明实施例1～3所得PDPPDTP-P、PDPPDTP-1-N、PDPPDTP-2-N以及对比例1、2所述聚合物所得有机光电探测器器件的光电性能测试结果见表1。
表1利用不同聚合物产物所得机光电探测器器件的光电性能测试结果
Figure BDA0002405953270000081
上述结果表明，本发明所得D-A型共轭聚合物可表现出较高的EQE和较低的暗电流，在有机光电探测器方面有着很大的潜力。
以上所述仅为本发明的较佳实施例，并不用以限制本发明。本发明所列举的各原料都能实现本发明，以及各原料的上下限取值、区间值都能实现本发明，在此不一一列举实施例。此外，申请人需要指出的是，在本发明的精神和原则之内，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

1.一种D-A型共轭聚合物，其特征在于，其结构式为：
Figure FDA0002405953260000011
式中，R为C16-C20的直链或支链烷基；X为苯基、1-萘基或2-萘基；n取值范围为70-200。
2.权利要求1所述D-A型共轭聚合物的制备方法，其特征在于，包括如下步骤：
1)以噻吩基吡咯并吡咯二酮、溴代烷烃为主要原料，进行一次溴代反应得化合物1；然后将其与N-溴代丁二酰亚胺进行二次溴代反应得化合物2，其结构式见式II；
Figure FDA0002405953260000012
2)以二噻吩并吡咯和三甲基氯化锡为主要原料进行卤代反应得化合物3，其结构式见式III；
Figure FDA0002405953260000013
3)将所得化合物2和化合物3，在保护气氛和催化剂作用下进行聚合反应，即得所述D-A型共轭聚合物。
3.根据权利要求2所述的制备方法，其特征在于，所述溴代烷烃的碳原子数为16～20。
4.根据权利要求2所述的制备方法，其特征在于，步骤1)中所述噻吩基吡咯并吡咯二酮与溴代烷烃的摩尔比为1:(2～2.5)；化合物1与N-溴代丁二酰亚胺的摩尔比为1:(2～2.5)。
5.根据权利要求2所述的制备方法，其特征在于，步骤1)中所述一次溴代反应温度为130～145℃，时间为12～18h；所述二次溴代反应温度为室温，条件为避光，时间为12h。
6.根据权利要求2所述的制备方法，其特征在于，步骤2)中所述二噻吩并吡咯和三甲基氯化锡的摩尔比为1:(2.5～3)。
7.根据权利要求2所述的制备方法，其特征在于，步骤2)中所述卤代反应温度为室温，时间为12～18h。
8.根据权利要求2所述的制备方法，其特征在于，所述化合物2与化合物3的摩尔比为1:1。
9.根据权利要求2所述的制备方法，其特征在于，步骤3)中所述聚合反应温度为100～110℃，时间为72～96h。
10.根据权利要求2所述的制备方法，其特征在于，所述二噻吩并吡咯的结构式见式IV；
Figure FDA0002405953260000021
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