CN112961326A - 一种萘并二呋喃共轭聚合物及其制备方法与应用 - Google Patents

一种萘并二呋喃共轭聚合物及其制备方法与应用 Download PDF

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CN112961326A
CN112961326A CN202110149028.1A CN202110149028A CN112961326A CN 112961326 A CN112961326 A CN 112961326A CN 202110149028 A CN202110149028 A CN 202110149028A CN 112961326 A CN112961326 A CN 112961326A
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difuran
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霍利军
郑冰
江雷
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Abstract

本发明公开了一种萘并二呋喃共轭聚合物及其制备方法，该聚合物具有如下分子式：
Figure DDA0002931490500000011
式中R代表氢原子或具有1‑30个碳原子的烷基；n代表聚合物的重复单元个数，为5‑1000之间的自然数，链段端基为R。基于本发明的萘并二呋喃共轭聚合物的器件可以得到大的共轭程度和高迁移率，在太阳能电池中展现出良好的膜厚耐受性，由其制备的太阳能电池具有较高的电池效率。

Description

一种萘并二呋喃共轭聚合物及其制备方法与应用
技术领域
本发明涉及一种萘并二呋喃共轭聚合物及其制备方法，具体涉及一种PNDF-T1聚合物在光电转换器件中的应用
背景技术
聚合物太阳能电池具有成本低、质量轻、可卷曲等优点，越来越多的科研工作者对此展开研究。由于聚合物给体和非富勒烯受体材料的不断更新，现有的太阳能电池的能量转换效率已经超过17％。但由于膜厚稳定性不足、空穴迁移率较低的问题，制约了聚合物太阳能电池的商业发展。为了解决这些问题，技术人员采用多稠环结构的供电子单元合成共轭聚合物，获得了较高的空穴迁移率，并且通过受体单元侧链的精细修饰和调节，使材料具有更好的膜厚耐受性。
对于充当电子给体的共轭聚合物材料来说，电荷迁移率是一个十分重要的物理参数，高电荷迁移率的材料往往可以使电池拥有更高的短路电流。此外，随着膜厚的增加，电池的器件效率会显著降低，在实验室器件中，活性层的厚度仅有100nm左右，较难的制备工艺制约了有机光伏的商业应用。因此寻找一种具有膜厚耐受性的材料是十分必要的。
萘并[2,3-b：6,7-b']二呋喃(NDF)拥有多稠环结构，在延长分子共轭结构的同时又增加了分子平面性，从而促进分子的堆积，增加材料的空穴迁移率。Masahiro Nakano(Chem.Mater.2012,24,190-198)等将萘并[2,3-b：6,7-b']二呋喃应用在有机场效应晶体管中(OFET)，发现此类材料有较高的电荷迁移率。同时对材料受体单元的侧链进行精细调整，能有效提高材料的膜厚耐受性，有利于有机光伏材料的商业应用。
发明内容
针对上述现有技术存在的问题，本发明提供了一种使用萘并二呋喃作为给体单元，长烷基取代的苯并二噻吩二酮作为受体单元合成的新型共轭聚合物，该共轭聚合物在电荷迁移率及膜厚耐受性方面具有优异的性能。本发明的技术方案如下：
一种萘并二呋喃共轭聚合物P1，聚合物分子式如下：
Figure BDA0002931490480000021
其中，R代表氢原子或具有1-30个碳原子的烷基；n代表聚合物的重复单元个数，为5-1000之间的自然数，链段端基为R。
优选的，R为2-己基癸基，聚合物分子式如下：
Figure BDA0002931490480000022
一种萘并二呋喃共轭聚合物P1的制备方法，将2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃和1,3-双(5-溴噻吩-2-基)-5,7-双(2-己基辛基)-4H，8H-苯并[1,2-c：4,5-c']二噻吩-4,8-二酮在四(三苯基膦)钯催化下，在100-120℃温度下反应，得到萘并二呋喃共轭聚合物P1。
优选的，所述2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃由如下步骤制备得到的：
(1)萘酚、液溴在醋酸和三氯化铁催化作用下反应得到1,3,5,7-四溴-2,6-二羟基萘；
(2)1,3,5,7-四溴-2,6-二羟基萘在醋酸与锡粉催化作用下反应得到3,7-二溴-2,6-二羟基萘；
(3)3,7-二溴-2,6-二羟基萘和乙酸酐在二氯甲烷和吡啶催化作用下反应得到3,7-二溴-2,6-双(乙酰)萘；
(4)3,7-二溴-2,6-双(乙酰)萘与三甲基硅基乙炔在二异丙胺、四三苯基膦钯和碘化亚铜催化作用下反应得到2,6-双(乙酰)-3,7-双(三甲基硅乙炔)萘；
(5)2,6-双(乙酰)-3,7-双(三甲基硅乙炔)萘与碳酸铯作用下关环反应得到萘并[2,3-b：6,7-b']二呋喃；
(6)萘并[2,3-b：6,7-b']二呋喃与三甲基氯化锡在二异丙氨基锂作用下反应得到2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃；
具体反应分子式如下：
Figure BDA0002931490480000031
一种萘并二呋喃共轭聚合物P1的应用，其用于制备太阳能电池电子给体材料。
本发明提供的萘并二呋喃共轭聚合物P1及其制备方法，具有以下有益效果：
(1)本发明将萘并二呋喃作为给体单元，长烷基取代的苯并二噻吩二酮作为受体单元，合成了新型的宽带隙的聚合物，这种线性的NDF结构有更大的共轭程度和高迁移率。
(2)本发明的萘并二呋喃共轭聚合物P1可用于太阳能电池电子给体材料的制备，可获得较高的有机太阳能电池效率。
(3)本发明的萘并二呋喃共轭聚合物P1在太阳能电池中展现出良好的膜厚耐受性。
(4)本发明的萘并二呋喃共轭聚合物P1结构中萘并二呋喃单元上未引入侧链结构，降低了材料合成的制作成本。
附图说明
参照附图以示例性而非限制性的方式详细描述本发明的一些具体实施例。附图中相同的附图标记标示了相同或类似的部件或部分。本领域技术人员应该理解，这些附图未必是按比例绘制的。本发明的目标及特征考虑到如下结合附图的描述将更加明显，附图中：
图1是本发明的萘并二呋喃共轭聚合物P1的紫外-可见吸收光谱。
图2是本发明的萘并二呋喃共轭聚合物P1的循环伏安特性曲线图。
图3是本发明的萘并二呋喃共轭聚合物P1与ITIC制成的光伏器件的J-V曲线图。
图4是本发明的萘并二呋喃共轭聚合物P1与ITIC制成的光伏器件的EQE曲线图
图5是本发明的萘并二呋喃共轭聚合物P1的仅空穴器件的的J-V曲线图。
具体实施方式
下面结合附图对本发明的具体实施方式进行详细说明，但并不用来限制本发明的保护范围。
(1)聚合物的合成
1,3,5,7-四溴-2,6-二羟基萘(2)
将2,6-二羟基萘(化学物1)(5g，31.2mmol)加入250mL烧瓶中并用100mL醋酸作为剂。加入7mL液溴后在120℃下回流反应12小时，然后再加入三氯化铁(0.38g,2.3mmol)和7mL液溴，120℃下回流反应12小时。反应结束后，冷却至室温并加入100mL的冰水，将生成物抽滤烘干后用1,4-二氧六环重结晶得到浅绿色固体。(11g,收率71％)1H NMR(400MHz,THF)δ8.35(s,2H)，8.96(s,2H)。
3,7-二溴-2,6-二羟基萘(3)
将化学物2(5g，10.5mmol)加入250mL烧瓶中并用100mL醋酸作为溶剂。向反应液中加入锡粉(2.5g，21mmol)，在120℃下回流反应75小时。反应结束后冷却至室温后，向混合物中加入100mL水。将产物过滤并用水洗涤，烘干后得到化学物8，为白色固体。(2.5g，75％)1HNMR(400MHz,DMSO)δ8.91(s,2H),8.56(d,2H),7.81(d,2H).
3,7-二溴-2,6-双(乙酰)萘(4)
将化合物3(3.2g，10mmol)加入到100mL烧瓶中并用40mL二氯甲烷作为溶剂。向反应液中加入2mL吡啶后，缓慢加入乙酸酐(5mL，60mmol)。在室温下反应15小时后，加入10mL水和10mL盐酸。用二氯甲烷萃取混合物三次并用无水硫酸镁干燥，将溶剂旋干后，粗产物用硅胶柱色谱法提纯，用二氯甲烷作为洗脱剂，得到白色固体。(2.5g,62％)1H NMR(400MHz,CDCl3)δ8.06(s,2H),7.52(s,2H),2.41(s,6H)。
2,6-双(乙酰)-3,7-双(三甲基硅乙炔)萘(5)
将化合物4(1g，2.5mmol)、12mL二异丙胺、四三苯基膦钯(150mg，0.13mmol)和碘化亚铜(120mg，0.63mmol)加入到100mL烧瓶中，用30mL二甲基甲酰胺溶解。鼓气十分钟后，缓慢加入三甲基硅基乙炔(0.35g，3.5mmol)并在室温下反应1小时。反应结束后加入5mL水和5mL盐酸，混合物用二氯甲烷萃取三次后用无水硫酸镁干燥。将旋干溶剂后，粗产物通过硅胶柱提纯，用石油醚作为洗脱剂，得到白色固体。(0.71g，65％收率)1H NMR(400MHz,CDCl3)δ7.93(s,2H),7.46(s,2H),2.37(s,6H),0.27(s,18H)。
萘并[2,3-b：6,7-b']二呋喃(6)
将化合物5(500mg，1.15mmol)加入到100mL的烧瓶中，并用30mLN，N-二甲基乙酰胺作为溶剂，加入6ml含有Cs2CO3(6.77g，22.70mmol)的水溶液。反应在80℃下搅拌24小时后，停止加热并冷却至室温，加入20ml水。混合物用二氯甲烷萃取三次后用无水硫酸镁干燥。将旋干溶剂后，粗产物通过硅胶柱提纯，用二氯甲烷作为洗脱剂，得到白色固体。(0.18g，75％)1H NMR(400MHz,CDCl3)δ8.14(s,2H),8.01(s,2H),7.71(d,2H),6.88(s,2H)。
2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃(7)
将萘并[2,3-b：6,7-b']二呋喃(0.6g，2.9mmol)加入到50mL烧瓶中并溶解在20mL四氢呋喃中。鼓气15分钟后，在-78℃下将二异丙氨基锂(2M，4mL)缓慢加入到反应液中，在-78℃下反应2小时。然后在-78℃下一次性加入三甲基氯化锡(1M，10mL)，缓慢恢复室温后反应过夜。反应终止后向混合液中加入10mL水，用乙醚萃取混合物三次并用无水硫酸镁干燥。将旋干溶剂后，用乙醇重结晶，得到白色晶体状固体(1.39g，收率90％)。1H NMR(CDCl3,400MHz),d(ppm):d7.97(s,2H),7.88(s,2H),6.92(t,J＝4.0Hz,2H),0.29(m,18H).13CNMR(CDCl3,25℃):δ168.4,156.1,128.9,128.5,117.2,117.0,105.8。
聚合物P1
将1,3-双(5-溴噻吩-2-基)-5,7-双(2-己基辛基)-4H，8H-苯并[1,2-c：4,5-c']二噻吩-4,8-二酮(140.25mg，0.15mmol)和化合物7(80.07mg，0.15mmol)加入50mL烧瓶中并溶解在8mL的甲苯中，用氮气鼓气10分钟。将四三苯基膦钯(8mg)加入烧瓶后，再鼓气10分钟。将反应液逐渐加热至110℃并在110℃和氮气氛围下反应16小时。反应结束后，停止加热并冷却至室温，将混合物沉降到60mL甲醇中并过滤。在真空烘箱中干燥后，粗产物通过硅胶柱提纯，得到产物。(65％收率)
(2)紫外-可见吸收测试
从图1中可见，P1在溶液和薄膜中的吸收峰分别在583和626nm。
(3)电化学测试
利用电化学工作站对该聚合物P1的电化学特性进行测试(参见图2)，P1的起始氧化电位(Eox)相对于Ag/Ag+为1.07eV。P1的起始还原电位(Ered)相对于Ag/Ag+为-1.01eV。因此，我们可以得到P1的HOMO和LUMO能级分别为-5.41eV和-3.62eV。
(4)器件的制备与表征
器件结构为ITO/ZnO/聚合物：ITIC/MoO3/Ag。依次用肥皂水、去离子水、丙酮和异丙醇超声清洗ITO玻璃基底,在110℃下真空干燥过夜后用臭氧处理20分钟。然后在清洗干净的ITO玻璃基底上将ZnO以4000rpm旋涂20秒并在200℃下退火30分钟。将具有不同浓度添加剂和给受体重量比P1和ITIC的混合物溶解在氯仿(CF)中，然后活性层以2000rpm旋涂40秒。待干后真空蒸镀MoO3电子传输层和Ag电极层。制得的太阳能电池器件由Keithley 2400在AM1.5G的模拟光下测得的光电转换效率为11.15％，开路电压Voc为0.85eV，短路电流密度Jsc＝17.39mA cm-2，填充因子FF＝0.753。同时，随着活性层膜厚增加至600nm，能量转化效率以然可以维持为10.85％。其中，太阳光模拟器是通过校准的硅太阳能电池来校正。EQE值则使用QEX10太阳能电池IPCE测量系统来测量。电流密度-电压(J-V)曲线和EQE曲线图见图3-4。通过采用空间电荷限制电流(SCLC)模型计算P1的空穴迁移率为2.61×10-3。
以上对本发明实施例所提供的技术方案进行了详细介绍，本文中应用了具体个例对本发明实施例的原理以及实施方式进行了阐述，以上实施例的说明只适用于帮助理解本发明实施例的原理；同时本领域的一般技术人员，根据本发明的实施例，在具体实施方式以及应用范围上均会有改变之处，综上，本说明书内容不应理解为对本发明的限制。

Claims (5)

1.一种萘并二呋喃共轭聚合物P1，其特征在于，聚合物分子式如下：
Figure FDA0002931490470000011
其中，R代表氢原子或具有1-30个碳原子的烷基；n代表聚合物的重复单元个数，为5-1000之间的自然数，链段端基为R。
2.根据权利要求1所述的萘并二呋喃共轭聚合物P1，其特征在于，R为2-己基癸基，聚合物分子式如下：
Figure FDA0002931490470000012
3.根据权利要求1或2所述的萘并二呋喃共轭聚合物P1的制备方法，其特征在于，将2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃和双(2-己基癸基)5,5”-二溴-[2,2'：5'，2”-三噻吩]-3,3”-二羧酸在四(三苯基膦)钯催化下，在100-120℃温度下反应，得到萘并二呋喃共轭聚合物P1。
4.根据权利要求3所述的制备方法，其特征在于，所述2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃由如下步骤制备得到的：
(1)萘酚、液溴在醋酸和三氯化铁催化作用下反应得到1,3,5,7-四溴-2,6-二羟基萘；
(2)1,3,5,7-四溴-2,6-二羟基萘在醋酸与锡粉催化作用下反应得到3,7-二溴-2,6-二羟基萘；
(3)3,7-二溴-2,6-二羟基萘和乙酸酐在二氯甲烷和吡啶催化作用下反应得到3,7-二溴-2,6-双(乙酰)萘；
(4)3,7-二溴-2,6-双(乙酰)萘与三甲基硅基乙炔在二异丙胺、四三苯基膦钯和碘化亚铜催化作用下反应得到2,6-双(乙酰)-3,7-双(三甲基硅乙炔)萘；
(5)2,6-双(乙酰)-3,7-双(三甲基硅乙炔)萘与碳酸铯作用下关环反应得到萘并[2,3-b：6,7-b']二呋喃；
(6)萘并[2,3-b：6,7-b']二呋喃与三甲基氯化锡在二异丙氨基锂作用下反应得到2,7-双(三甲基锡烷基)萘并[2,3-b：6,7-b']二呋喃。
5.根据权利要求1-4之一所述的萘并二呋喃共轭聚合物P1的应用，其特征在于，其用于制备太阳能电池电子给体材料。
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