CN105622902A - 一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物及其制备方法 - Google Patents

一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物及其制备方法 Download PDF

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CN105622902A
CN105622902A CN201610190323.0A CN201610190323A CN105622902A CN 105622902 A CN105622902 A CN 105622902A CN 201610190323 A CN201610190323 A CN 201610190323A CN 105622902 A CN105622902 A CN 105622902A
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thiophene
alkyl
bithiophene
diazosulfide
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杜俊平
陈凤华
方少明
田俊峰
李皓
李臻
张亚芳
李闯
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Zhengzhou University of Light Industry
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Abstract

本发明涉及一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物及其制备方法，属聚合物光电功能材料设计合成领域。该共轭聚合物具有如下的结构单元：其中，R1为氢原子、C6-C20的烷基；R2为氢原子、氟原子、C6-C20的烷基或烷氧基，R3为C6-C20的烷基，n=2-60。该类聚合物以商品化的双噻吩苯并噻二唑二锡单体，双噻吩吡咯并吡咯二溴单体为反应原料，采用微波协助的Stille缩合聚合反应的方法快速高效制备。本发明结合噻吩、吡咯并吡咯和苯并噻二唑这三种单元的优点，提供一种新型的基于这三种单元的共轭聚合物材料。该聚合物有望应用于有机薄膜晶体管和有机光伏器件中的活性材料。

Description

一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物及其制备方法
技术领域
本发明属于聚合物光电功能材料设计合成技术领域，特别涉及一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物及其制备方法。
背景技术
自从上世纪70年代导电聚合物发现以来，新型导电聚合物的设计合成及应用研究引起了世界各国产业界和科学界的广泛关注。尽管与传统的无机材料相比，该类材料具有质量轻、成本低、柔韧性好，并且可以采用廉价的溶液加工方式加工，可制备成柔性可折叠器件等无可比拟的优点，并且以该类材料为活性材料的光电器件如有机电致发光二极管、有机场效应晶体管、有机太阳能电池等已在显示、照明、能源等领域显示了诱人的应用前景，然而，该类材料的商品化和实用化，仍有赖于产品性能的进一步提高。在共轭聚合物的设计合成中，一方面，已有报道表明四噻吩单元的引入有助于提高聚合物材料的结晶度，减小聚合物堆积间距，从而提高材料的电荷传输性能(Polym.Chem.2015,6,6050；Adv.Mater.2012,24,6164；J.Am.Chem.Soc.2012,134,3498.)另一方面，苯并噻二唑单元和吡咯并吡咯单元是两类高效的受体单元，已被广泛应用于共轭聚合物材料的构筑中(J.Am.Chem.Soc.2015,137,1314；Nat.Photo.2012,6,180；J.Am.Chem.Soc.2012,134,10071；Adv.Mater.2013,25,825；J.Am.Chem.Soc.2013,135,13549；Nat.Commun.2013,4,1446；Angew.Chem.Int.Ed.2012,51,2020；Mater.Today.2015,18,425.)。然而，基于四噻吩单元、苯并噻二唑单元和吡咯并吡咯单元的聚合物仍未见报道。基于此，本发明设计合成了基于这三种单元的聚合物材料，并通过烷基侧链的引入提高材料的溶液加工性能，芳环上取代基的不同调节材料的性能，以期获得高性能的共轭聚合物材料，用于有机电子器件的活性材料尤其是有机场效应晶体管材料和有机太阳能电池材料。
发明内容
结合苯并噻二唑单元、吡咯并吡咯单元和噻吩单元的优点，本发明的目的在于提供一种可溶性的双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物；另一目的在于提供一种简单易行、高效快速的该共轭聚合物的合成方法。
为实现本发明目的，本发明以四噻吩单元作为供体单元，以苯并噻二唑单元和吡咯并吡咯单元作为受体单元，设计合成了基于这三种单元的共轭聚合物材料，可用于有机电子器件的活性材料尤其是有机场效应晶体管和有机太阳能电池的活性材料。
所述共轭聚合物材料具有如下结构单元：
上式中，R1为氢原子、C6-C20的烷基；R2为氢原子、氟原子、C6-C20的烷基或烷氧基；R3为C6-C20的烷基，n＝2-60。
优选：R1为氢原子、C6-C8的烷基；R2为氢原子、氟原子、C6-C8的烷基；R3为C18-C20的烷基，n＝2-60。
R1所述烷基优选直链烷基；R2所述烷基优选直链烷基，烷氧基优选直链烷氧基；R3烷基优选支链烷基。
所述共轭聚合物材料通过以下方法实现：
氮气环境下，有机溶剂中，分别以双卤代单体化合物2和双有机锡单体化合物1为原料，在金属催化剂的作用下，采用经典的Stille缩合聚合反应法，运用微波加热反应得到所述的聚合物。反应式如下：
其中，R1为氢原子、C6-C20的烷基；R2为氢原子、氟原子、C6-C20的烷基或烷氧基；R3为C6-C20的烷基；R4为C1-C4的烷基；X为溴或碘；n＝2-60。
聚合物反应中化合物1和化合物2的摩尔比为1：1-1.2。
优选的，步骤中所述双有机锡单体化合物和双溴单体化合物结构如下所示：
其中，R1为氢或C6-C20烷基；R2为氢、氟、C6-C20的烷基或烷氧基；R3为C6-C20的烷基。
所述有机钯催化剂选醋酸钯、四(三苯基膦)钯、Pd2(dba)3/P(o-Tol)；有机镍催化剂选Ni(dppp)Cl2。优选四(三苯基磷)钯。催化剂的用量相当于化合物1摩尔数的0.1-20mol％。
优选的，所述的微波升温方法为程序升温，升温方法为：室温搅拌0-60秒，80-100℃下反应2-10分钟，100-120℃下反应2-10分钟，120-200℃下反应10-60分钟。
所述有机溶剂为甲苯、二甲苯、氯苯、二氯苯或三氯苯，优选邻二甲苯。
本发明具有如下有益效果：一方面，本发明设计了一种新型的导电聚合物材料，该材料结合了噻吩单元、苯并噻二唑单元和吡咯并吡咯单元三种单元的优点，苯并噻二唑单元和吡咯并吡咯单元的同时引入使聚合物的紫外吸收发生深度红移，有利于提高太阳光吸收效率，结构中的四个噻吩单元有利于进一步改善材料的电荷传输性能，侧链柔性烷基链可以调节材料的溶液加工性能，另外，芳环上取代基的不同可以微调材料的性质。本发明所制得的共轭聚合物材料有望成为一类新型的高性能的有机光电功能材料，尤其是作为有机太阳能电池材料和有机场效应晶体管材料。另一方面，本发明采用微波协助Stille缩合聚合反应方法具有简单易行，高效快速的特点，可推广应用新型共轭聚合物材料的合成中。
附图说明
图1为实施例1合成的聚合物P1的FT-IR图谱；
图2为实施例2合成的聚合物P2的FT-IR图谱；
图3为实施例3合成的聚合物P3的FT-IR图谱；
图4为本发明聚合物P1、P2和P3在氯苯溶液中的紫外吸收光谱图；
图5为本发明聚合物P1、P2和P3的TGA图。
具体实施方式
下面结合附图对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1聚合物P1的合成
氮气环境下，10mL微波反应瓶中，加入单体化合物1(313.01mg，0.5mmol)(此时R1＝H，R2＝H，R4＝CH3)，单体化合物2(509.61mg，0.5mmol)(X＝Br，R3＝CH2CH(C8H17)(C10H21))，Pd(PPh3)4(5.78mg，0.005mmol)和邻二甲苯4ml，微波反应器中升温反应：90℃，10min；100℃，10min；170℃，40min；得到深蓝色黏稠物。反应液甲醇沉淀，所得固体分别用甲醇、丙酮、正己烷、氯仿、氯苯索氏提取，收集氯仿和氯苯提取物，分别再次甲醇沉淀，真空干燥得蓝色固体产物0.41g(氯仿提取物)，70mg(氯苯提取物)。总产率：83％。MolecularWeight(GPC,eluent＝chlorobenzene,detector＝RI):Mn,2500(chloroformfraction)FT-IR(NaCl):3071,2928,2847,1663,1548,1432,1398,1226,1018,880,788,725。
实施例2聚合物P2的合成
氮气环境下，10mL微波反应瓶中，加入单体化合物1(313.01mg，0.5mmol)(此时R1＝H，R2＝F，R4＝CH3)，单体化合物2(509.61mg，0.5mmol)(X＝Br，R3＝CH2CH(C8H17)(C10H21))，Pd(PPh3)4(5.78mg，0.005mmol)和邻二甲苯4ml，微波反应器中反应，80℃，10min；120℃，10min；200℃，30min；反应液甲醇沉淀，所得固体分别用甲醇、丙酮、正己烷、氯仿、氯苯索氏提取，收集氯仿和氯苯提取物，再次甲醇沉淀，真空干燥后得产物为蓝色固体0.21g(氯仿提取物)，30mg(氯苯提取物)。总产率：40％。MolecularWeight(GPC,eluent＝chlorobenzene,detector＝RI):Mn,3050(chloroformfraction)FT-IR(NaCl):3066,2928,2847,1663,1547,1427,1254,1226,1024,852,788,731.
实施例3聚合物P3的合成
氮气环境下，10mL微波反应瓶中，加入单体化合物1(313.01mg，0.5mmol)(此时R1＝C6H13，R2＝F，R4＝CH3)，单体化合物2(509.61mg，0.5mmol)(X＝Br，R3＝CH2CH(C8H17)(C10H21))，Pd(PPh3)4(5.78mg，0.005mmol)和邻二甲苯4ml，微波反应器中反应，100℃，5min；110℃，5min；130℃，60min；得蓝色黏稠物。反应液甲醇沉淀，所得固体分别用甲醇、丙酮、正己烷、氯仿、氯苯索氏提取，收集氯仿和氯苯提取物，再次甲醇沉淀，真空干燥得蓝色固体产物0.29g(氯仿提取物)，80mg(氯苯提取物)。总产率：54％。MolecularWeight(GPC,eluent＝chlorobenzene,detector＝RI):Mn,5961(chloroformfraction)FT-IR(NaCl):3070,2922,2852,1660,1550,1425,1323,1230,1074,855,809,730.
所得聚合物P1、P2和P3的结构如表1所示
表1
聚合物P1、P2和P3所述R1＝C6H13为直链烷基，R3中C8H17，C10H21为直链烷基。
图4给出了聚合物P1、P2和P3在氯苯溶液中的紫外吸收光谱图，从图中可以看出，三种聚合物在氯苯溶液中的最大吸收峰的位置分别为：721nm,692nm,705nm，在400nm-1000nm范围内都有不同程度的吸收，光学带宽分别为：1.338，1.343,1.305，说明聚合物可能具有较高的太阳光吸收效率。
图5给出了聚合物P1、P2和P3TGA图，从图中可以看出，优选的三种聚合物的5％热失重温度均大于378℃，说明聚合物具有较高的热稳定性能。
聚合物易溶于邻二甲苯、氯苯、二氯苯等溶剂中，方便用廉价的溶液加工方法制备电子器件。
该类材料有望用作有机电子器件的活性材料尤其是有机场效应晶体管和有机太阳能电池的活性材料。

Claims (9)

1.一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物，其特征在于，所述的共轭聚合物是基于双噻吩苯并噻二唑单元和双噻吩吡咯并吡咯单元的共轭聚合物，其具有如下结构单元：
上式中，R1为氢原子或C6-C20的烷基；R2为氢原子、氟原子、C6-C20的烷基或烷氧基；R3为C6-C20的烷基，n=2-60。
2.如权利要求1所述的一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物，其特征在于：R1为氢原子、C6-C8的烷基；R2为氢原子、氟原子或C6-C8的烷基；R3为C18-C20的烷基，n=2-60。
3.如权利要求1或2所述的一类基于双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物，其特征在于：R1所述烷基选直链烷基；R2所述烷基选直链烷基，烷氧基选直链烷氧基；R3烷基选支链烷基。
4.如权利要求3所述的一类基于双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物，其特征在于：选如下化合物之一：
。
5.制备如权利要求1所述的一类双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物的方法，其特征在于：合成方法如下：
氮气环境下，有机溶剂中，分别以双卤代单体化合物2和双有机锡单体化合物1为原料，在有机钯催化剂或有机镍催化剂的作用下，采用经典的Stille缩合聚合反应法，微波加热反应得到所述的聚合物；
上式中，R1为氢原子、C6-C20的烷基；R2为氢原子、氟原子、C6-C20的烷基或烷氧基；R3为C6-C20的烷基；R4为C1-C4的烷基；X为溴或碘；n=2-60；
所述有机溶剂为甲苯、二甲苯、氯苯、二氯苯或三氯苯。
6.根据权利要求5所述的双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物的制备方法，其特征在于：所述有机钯催化剂选醋酸钯、四（三苯基膦）钯、Pd2(dba)3/P（o-Tol）；有机镍催化剂选Ni(dppp)Cl2。
7.根据权利要求5所述的双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物的制备方法，其特征在于：所述微波升温方法为程序升温，升温方法为：室温搅拌0-60秒，80-100℃下反应2-10分钟，100-120℃下反应2-10分钟，120-200℃下反应10-60分钟。
8.根据权利要求5所述的双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物的制备方法，其特征在于：聚合物反应中化合物1和化合物2的摩尔比为1：1-1.2。
9.根据权利要求5所述的双噻吩苯并噻二唑-双噻吩吡咯并吡咯共轭聚合物的制备方法，其特征在于：催化剂的用量相当于化合物1摩尔数的0.1-20mol%。
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