CN113801302B - 基于a-d-a’-d-a型引达省并噻吩衍生单元非共轭聚合物及其制备方法 - Google Patents
基于a-d-a’-d-a型引达省并噻吩衍生单元非共轭聚合物及其制备方法 Download PDFInfo
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- CN113801302B CN113801302B CN202111207772.9A CN202111207772A CN113801302B CN 113801302 B CN113801302 B CN 113801302B CN 202111207772 A CN202111207772 A CN 202111207772A CN 113801302 B CN113801302 B CN 113801302B
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Abstract
本发明涉及基于A‑D‑A’‑D‑A型引达省并噻吩衍生单元非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，R为C2～C18烷基，X可取1~12，n≥1。聚合物主链A‑D‑A’‑D‑A结构呈平面性刚性骨架，将SP3杂化的非共轭烷基链引入聚合物分子主链使本发明在四氢呋喃、氯仿、氯苯等有机溶剂可充分溶解，为其溶液加工成膜创造了基础条件。本发明中的基于A‑D‑A’‑D‑A型引达省并噻吩衍生单元非共轭聚合物具有在可见‑近红外区宽而强的吸收。本发明作为半导体活性层受体材料在聚合物太阳能电池器件中有潜在的应用前景，有望获得高的太阳能电池的光电转化效率。
Description
技术领域
本发明涉及一种在可见-近红外区有强吸收的聚合物受体材料及其制备方法，属于聚合物太阳能电池受体材料领域。
背景技术
聚合物太阳能电池具有材料种类多、可设计性强、易于溶液加工、可大面积生产和可制备柔性器件等一系列优势，已成为学术界的研究热点。制约全聚合物太阳能电池发展的主要瓶颈是高性能聚合物受体材料的缺乏。设计合成高性能聚合物受体成为推动全聚合物太阳能电池器件效率实现突破的重要途径。(参见文献：Cui Y,Yao H,Hong L,etal.Organic photovoltaic cell with 17％efficiency and superior processability,NATL SCI REV,7:1239-46(2020))。
基于氰基茚酮类结构单元的聚合物受体受到关注。这类聚合物受体通常可以在可见-近红外光区域具有强的吸收峰。这类聚合物受体的设计策略是将氰基茚酮类小分子受体衍生单元用简单的π共轭结构单元进行共价键连，形成共轭聚合物。其中，氰基茚酮类小分子受体衍生单元通常是梯形稠环共轭单元。问题在于这种梯形稠环共轭单元形成共轭聚合物后其溶解性、溶液加工性以及分子量等受到影响。本发明从分子设计上进行优化，构建具有良好溶解性与溶液加工性以及分子量高的高性能氰基茚酮类小分子受体衍生单元。(参见文献：Zhang J,Tan H S,Guo X,Material insights and challenges for non-fullerene organic solar cells based on small molecular acceptors,Nat.Energy,3:720-31(2018))。
发明内容
本发明的目的是提供一种可溶液加工的A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物及其制备、用途。本发明聚合物主链A-D-A’-D-A结构呈平面性刚性骨架，将SP3杂化的非共轭烷基链引入聚合物分子主链使本发明在四氢呋喃、氯仿、氯苯等有机溶剂可充分溶解。该聚合物在可见-近红外区具有强吸收，在聚合物太阳能电池器件中有潜在的应用前景。
本发明的目的是通过以下的技术方案实现的：
第一方面，本发明涉及一种A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物，结构中A(Acceptor)为氰基茚酮单元，D(Donor)为引达省并噻吩衍生单元。
所述共轭聚合物的结构式如下所示：
第二方面，本发明涉及一种制备上述的A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的方法，包括如下步骤：
a、将醛基端基结构的中间体N，在有机溶剂中与溴代氰基茚酮进行knoevenagel反应，得到溴代氰基茚酮为端基的A-D-A’-D-A型引达省并噻吩单体M；
b、将溴代氰基茚酮为端基的A-D-A’-D-A型引达省并噻吩单体M与二甲基锡共轭单体Y在催化剂和配体的作用下，在无水有机溶剂中共聚，索氏提取得到所述的共轭聚合物。
优选地，步骤a中，所述中间体N的结构式如下所示：
所述单体M的结构式如下所示：
R为C2～C18烷基。
优选地，步骤b中，所述二甲基锡共轭单体Y的结构式如下所示：
优选地，所述步骤a具体为：将中间体N与溴代氰基茚酮以有机溶剂为介质，在碱性催化剂催化下进行反应；以体积比为1:(0.5～10)的石油醚和二氯甲烷为洗脱剂，洗脱得到溴代氰基茚酮为端基的A-D-A’-D-A型引达省并噻吩单体M。
进一步优选地，所述有机溶剂为三氯甲烷，碱性催化剂为吡啶。
优选地，所述步骤a具体为：所述反应时间为0.5～48小时,反应温度为25～85℃。
优选地，步骤b中，所述共聚的反应时间为0.5～48小时,反应温度为60～120℃。
优选地，步骤b中，所述无水有机溶剂为无水甲苯、无水氯苯或四氢呋喃。
优选地，步骤b中，所述催化剂为三(二亚苄基丙酮)二钯、配体为三邻甲苯基膦。
优选地，步骤b中，所述索氏提取依次采用的溶剂为甲醇、正己烷和氯仿或者正己烷和氯苯。
第三方面，本发明涉及一种前述的A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物在制备聚合物太阳能电池中的用途，所述非共轭聚合物作为聚合物太阳电池中的半导体有机层。
本发明具有如下的有益效果：本发明披露的合成方法简单、合成路线短而有效；原料易于制备，目标产物纯度高；将SP3杂化的非共轭烷基链引入聚合物分子主链使本发明在四氢呋喃、氯仿、氯苯等有机溶剂可充分溶解，为其溶液加工成膜创造了基础条件；本发明A-D-A’-D-A型结构以氰基茚酮为A(Acceptor)单元，引达省并噻吩衍生单元为D(Donor)单元，呈现平面分子的骨架且结构中缺电子单元苯并噻二唑(BT)核，增加D-A相互作用，增强分子间和分子内相互作用，有效地提高最高占据的分子轨道HOMO能级；本发明在可见-近红外区具有强吸收，可以应用于聚合物太阳能电池器件。
附图说明
图1为本发明实施例1中的单体M的合成路线图。
图2为本发明实施例1中的聚合物P的合成路线图。
图3为本发明实施例1中的中间体N的核磁共振氢谱。
图4为本发明实施例1中的单体M的核磁共振氢谱。
图5为本发明实施例1中的聚合物P的核磁共振氢谱。
图6为本发明实施例2中的聚合物P的凝胶渗透色谱GPC图。
图7为本发明实施例3中聚合物P的紫外可见光谱图。
图8为本发明实施例3中聚合物P的CV曲线图。
图9为本发明实施例2中聚合物P的热重曲线图。
图10为聚合物P作为半导体活性层受体材料的聚合物太阳能电池器件结构示意图。
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A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备
本实施例提供1种基于基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物，其合成路线参见图1。
1.1、单体M的制备
单体M的制备具体包括以下步骤：
(a)中间化合物N的合成
中间化合物N的结构式为
在氩气气氛下，将甲苯(3mL)，K2CO3溶液(2M，1.6mL)，H2O(1.2mL)加入耐压管中，液面下鼓泡20分钟后，依次加入4,7-双(4,4,5,5-四甲基-1,3,2-二氧杂戊硼烷-2-基)-2,1,3-苯并噻二唑(0.23mmol)，7-溴-4,4,9,9-四(4-己基苯基)-S-苯并二茚并[1,2-B:5,6-B']二噻吩-2-醛(0.50mmol)，Aliquat 336(2滴)，室温下搅拌10分钟，最后加入Pd(PPh3)4(0.012mmol)，再于液面上鼓泡10分钟。混合物在80℃下搅拌24小时，TLC跟踪反应进程。冷却至室温，用冰水淬灭反应。用二氯甲烷萃取反应混合物，有机相用水洗涤。无水硫酸钠干燥有机相。过滤，将滤液旋蒸浓缩。通过柱色谱法以石油醚：二氯甲烷体积比为1：1为洗脱剂纯化固体，得到粗产物。粗产物在甲醇溶剂中重结晶。真空干燥收集黑色固体，即中间体N(产率：76％)。
其中，7-溴-4,4,9,9-四(4-己基苯基)-S-苯并二茚并[1,2-B:5,6-B']二噻吩-2-醛的合成参考文献：《David F.,Kung-Shih Chen,Hin-Lap Yip,Yong Zhang,Alex K.-Y.,Tunable Light-Harvesting Polymers Containing Embedded DipolarChromophores forPolymer Solar Cell Applications,Polym.Chem.,50,1362–1373(2012)》。
(b)单体M的合成
单体M的结构式为
氩气气氛中，将中间体N(1mmol)、溴代氰基茚酮(CAS:2177251-91-9)(3mmol)和三氯甲烷(15mL)依次加入双口圆底烧瓶中，液面下鼓泡15分钟。将中间体A和溴代氰基茚酮充分溶解后，加入碱性催化剂吡啶(0.3mL)。温度设置在65℃下，进行避光反应。TLC跟踪反应进程，反应16小时结束。用二氯甲烷萃取反应混合物，所得有机相用水洗涤三次。用无水硫酸钠进行干燥有机相。过滤，先将滤液旋蒸浓缩。通过柱色谱法以石油醚：二氯甲烷体积比为1：1为洗脱剂纯化产物，得到粗产物。粗产物以甲醇溶剂重结晶。真空干燥收集黑色固体，即单体M(产率：45％)。
1.2、聚合物P的合成
聚合物P的结构式为
R＝—C6H13，X＝3，n≥1。
本发明对非共轭聚合物的反应条件进行了严格把控，聚合反应的浓度控制在大约2.5×10-2mol/L，采用无水甲苯作为溶剂。此外，依据反应实验现象对反应时间进行优化。最终优化结果如下：
在氩气保护下，单体M(0.04mmol)，1,6-双(5-(三甲基甲锡烷基)噻吩-2-基)己烷(0.04mmol)和1.6mL甲苯依次加入100mL的干燥Schlenk瓶中，氩气吹扫气下鼓泡除氧30分钟，再加入Pd2(dba)3(0.8mg，2mol％)和P(o-Tolyl)3(1mg，8mol％)。将封口的反应管置于油浴中缓慢加热至90℃下进行搅拌反应50分钟，体系黏稠度增大(内壁伴有固体析出)，聚合反应停止。将反应管冷却至室温，加入甲醇沉淀出粗产物，过滤，然后依次通过用石油醚、乙酸乙酯和氯仿进行索氏提取。其中，氯仿提取部分通过减压除去溶剂再进行甲醇二次沉淀后，进行真空干燥得到黑色固体，即目标聚合物P(产率：97％)。
其中，1,6-双(5-(三甲基甲锡烷基)噻吩-2-基)己烷结构式如下所示：
实施例2、聚合物P的凝胶渗透色谱、紫外吸收光谱和电化学性质
图6给出了聚合物P的凝胶渗透色谱GPC测得的数均分子量为20.98KDa，重均分子量为67.20KDa，分布系数PDI为3.20。图7给出了聚合物P在氯苯溶液和固体薄膜时的的紫外吸收光谱，它在溶液和薄膜的最大吸收峰分别位于680nm和697nm，光学带隙为1.56eV。图8给出了聚合物P的循环伏安曲线。电化学测试为三电极体系:工作电极即铂电极，辅助电极为铂丝电极，参比电极为Ag/AgNO3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100mVs-1，测试样品前后以二茂铁(Fc/Fc+)作为外标。，根据公式可计算其能级与能隙：EHOMO＝-(Eox onset+4.71)eV，ELUMO＝-(Ered onset+4.71)eV，Eg＝ELUMO-EHOMO，其中Eox onset是起始氧化电势，Ered onset是起始还原电势。电化学测试显示它的起始还原电位在-0.87eV左右，由此计算的LUMO能级为-3.84eV；起始还原氧化电位在0.75eV左右，由此计算的HOMO能级为-5.46eV。图9表明聚合物P具有良好的热稳定性。
实施例3、聚合物P作为半导体活性层受体材料在聚合物太阳能电池器件中的用途
图10给出了以聚合物P作为半导体活性层受体材料的聚合物太阳能电池器件的结构示意图。选用PBDB-T和PM6作为给体材料，分别与聚合物P双组分共混作为活性层，来组建聚合物太阳能电池器件研究其光伏性能。器件结构：ITO/ZnO/共混层/PFNBr/Ag。其中，将空穴缓冲层为ZnO，电子传输层为水溶性聚芴衍生物。表1给出了器件测试结果，以PBDB-T作为给体材料，器件光电转化效率(PCE)为0.79％，短路电流(Jsc)为2.17mA/cm2，开路电压(Voc)为提高到0.94V；以PM6作为给体材料，器件光电转化效率(PCE)为0.61％，短路电流(Jsc)为1.65mA/cm2，开路电压(Voc)为提高到0.97V。
综上所述，本发明涉及的A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物，结构特征是将SP3杂化的非共轭烷基链引入聚合物分子主链，其具有良好的溶液加工性能，将其作为聚合物受体材料应用于聚合物太阳能电池器件测试表明，基于PBDB-T：P的器件光电转化效率为0.79％。进一步调控匹配的给体材料及器件优化，有望得到更佳的光电转化效率。
表1
| 活性层材料 | V<sub>oc</sub>(V) | J<sub>sc</sub>(mAcm<sup>-2</sup>) | FF | PCE(％) | R<sub>s</sub>(Ωcm<sup>2</sup>) | R<sub>sh</sub>(Ωcm<sup>2</sup>) |
| PBDBT：P | 0.94 | 2.17 | 0.39 | 0.79 | 1723.64 | 11915.84 |
| PM6：P | 0.97 | 1.65 | 0.38 | 0.61 | 3638.81 | 17610.95 |
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (8)
1.一种基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物，其特征在于，所述共轭聚合物的结构式如下所示：
2.如权利要求1所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备方法，其特征在于，包括如下步骤：
a、将醛基端基结构的中间体N，在有机溶剂中与溴代氰基茚酮进行knoevenagel反应，得到A-D-A’-D-A型引达省并噻吩衍生单元单体M；
b、将A-D-A’-D-A型引达省并噻吩衍生单元单体M与二甲基锡非共轭单体Y在催化剂和配体的作用下，在无水有机溶剂中共聚，索氏提取得到所述的非共轭聚合物；
步骤a中，所述中间体N的结构式如下所示：
所述单体M的结构式如下所示：
步骤b中，所述二甲基锡非共轭单体Y的结构式如下所示：
3.根据权利要求2所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备方法，其特征在于，所述步骤a具体为：将中间体N与溴代氰基茚酮以有机溶剂为介质，在碱性催化剂催化下进行反应0.5～48小时,反应温度为25～85℃；以体积比为1:(0.5～10)的石油醚和二氯甲烷为洗脱剂，洗脱得到溴代氰基茚酮为端基的A-D-A’-D-A型引达省并噻吩衍生单元单体M。
4.根据权利要求3所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备方法，其特征在于，所述有机溶剂为三氯甲烷，所述碱性催化剂为吡啶。
5.根据权利要求2所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备方法，其特征在于，步骤b中，所述共聚的反应时间为0.5～48小时,反应温度为60～120℃。
6.根据权利要求2所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备方法，其特征在于，步骤b中，所述催化剂为三(二亚苄基丙酮)二钯、配体为三邻甲苯基膦。
7.根据权利要求2所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物的制备方法，其特征在于，所述无水有机溶剂为无水甲苯、无水氯苯或四氢呋喃；所述索氏提取依次采用的溶剂为甲醇、正己烷和氯仿或者正己烷和氯苯。
8.如权利要求1所述的基于A-D-A’-D-A型引达省并噻吩衍生单元非共轭聚合物在制备聚合物太阳能电池中的用途，其特征在于，所述非共轭聚合物作为聚合物太阳能电池中的半导体活性层受体材料。
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| CN108794511A (zh) * | 2018-08-02 | 2018-11-13 | 兰州大学 | 基于苯并二噻吩的衍生物、宽带隙小分子给体及其制备方法和应用 |
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| CN113387965A (zh) * | 2021-06-17 | 2021-09-14 | 南京邮电大学 | 一种有机电子受体材料及其制备方法与应用 |
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| KR20190117086A (ko) * | 2018-04-06 | 2019-10-16 | 주식회사 엘지화학 | 화합물 및 이를 포함하는 유기 태양 전지 |
| CN108794511A (zh) * | 2018-08-02 | 2018-11-13 | 兰州大学 | 基于苯并二噻吩的衍生物、宽带隙小分子给体及其制备方法和应用 |
| CN113387965A (zh) * | 2021-06-17 | 2021-09-14 | 南京邮电大学 | 一种有机电子受体材料及其制备方法与应用 |
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