CN107474226A - 一类全氟烷基修饰的苝酰亚胺共轭聚合物及其合成方法 - Google Patents
一类全氟烷基修饰的苝酰亚胺共轭聚合物及其合成方法 Download PDFInfo
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Abstract
一类全氟烷基修饰的苝酰亚胺共轭聚合物及其合成方法,结构通式为:以1,7‑二溴全氟烷基苝酰亚胺与双锡试剂为原料,摩尔比1:1,按溶剂与原料摩尔比300~400:1、催化剂与原料摩尔比0.02~0.1:1,无水无氧和溶剂的回流温度条件下,stille偶联反应。本发明可显著增加聚合物在有机溶剂中的溶解性,形成有序结晶或液晶结构,易于载流子传输,得到高迁移率,同时增强其光热稳定性和在场效应晶体管中的器件稳定性。
Description
技术领域
本发明属于有机化工和精细化工领域,具体涉及一类全氟烷基修饰的苝酰亚胺共轭聚合物及其合成方法。
背景技术
有机半导体是一类具有柔性,可低成本加工的光电子材料,在光电应用上有着诱人的前景。聚合物半导体材料因其好的稳定性,并且在器件制备中成膜性好,近20年发展迅速,在有机太阳能电池的应用已达到了超13%的光电转换效率(J.Am.Chem.Soc.2017,139,7302-7309)。苝酰亚胺(PDIs)作为受体材料因其具有大的共辄体系和良好的稳定性被广泛应用于有机半导体器件,但是PDIs差的溶解性,一直制约着它的应用。苝酰亚胺类聚合物半导体材料在有机太阳能器件中运用广泛,光电转换效率已达到8.59%(Adv.Mater.2017,1700309)。但是由于PDIs溶解性差,导致苝酰亚胺类聚合物分子量普遍偏低(数均分子量Mn小于40kDa),是其器件迁移率不高的一个重要原因。
全氟烷基具有刚性棒状结构,氟原子可以与邻近的氢原子形成分子间氢键,增强分子之间的相互作用(中国专利,公开号:CN106832246A),使得含氟原子及全氟烷基化合物具有极高的稳定性、抗氧化性和憎水性。氟原子或全氟烷基已经在有机光电领域被广泛应用,比如氟原子被用于高效体相异质结电池的受体材料(中国专利,公开号:CN106588923A),全氟烷基被用于构建空气稳定的场效应晶体管材料(Chem.Rev.2011,112,2208-2267)。含全氟烷基的聚合物易于形成有序的结晶或液晶结构,此类结构利于载流子的传输。全氟烷基修饰的非共轭聚合物有很多,它们能形成规则的有序堆积(中国专利,公开号:CN106588923A)。而在苝酰亚胺的N端直接引入全氟烷基修饰,会导致PDIs溶解性很差(中国专利,公开号:CN101289447B),使得溶液加工,器件成膜性方面出现障碍。基于此,我们需要开发出一类能溶液加工、成膜性能好、稳定性高、载流子迁移率高的苝酰亚胺共轭聚合物半导体材料。
发明内容
本发明的目的是合成一类全氟烷基修饰的苝酰亚胺共轭聚合物,以提高苝酰亚胺类共轭聚合物的溶解性,以及研究全氟烷基对该类聚合物的结晶性能、分子排列、能级、稳定性、载流子迁移率和太阳能电池或场效应晶体管器件性能的影响。
本发明是通过以下技术方案实现的。
本发明所述的一类全氟烷基修饰的苝酰亚胺共轭聚合物,其结构通式为:
R为全氟烷基链,结构式如下:
其中:m、n分别是烷基C原子的个数和全氟烷基C原子的个数,m是1、2、3、4、5、6,n是1、3、5、7。
Ar为噻吩,结构式如下:
并二噻吩:
联二噻吩:
并三噻吩:
联三噻吩:
BDT单元:
PBDTT单元:
IDT单元:
本发明所述的一类全氟烷基修饰的苝酰亚胺共轭聚合物的合成方法,其特征在于:
以1,7-二溴全氟烷基苝酰亚胺与双锡试剂为原料,摩尔比为1:1,按溶剂与原料摩尔比300~400:1的量、催化剂与原料摩尔比0.02~0.1:1的量,加入溶剂和催化剂,无水无氧和溶剂的回流温度条件下,进行stille偶联反应,生成含全氟烷基修饰的苝酰亚胺共轭聚合物。
所述的1,7-二溴全氟烷基苝酰亚胺,按中国专利(公开号:CN106588924A)制备。
所述的双锡试剂为噻吩双锡、并二噻吩双锡、联二噻吩双锡、并三噻吩双锡、联三噻吩双锡、BDT双锡、PBDTT双锡或IDT双锡。
所述的溶剂为氯苯、甲苯、三氟甲苯或DMF。
所述的催化剂为Pd2(dba)3/P(o-tol)3、Pd(PPh3)2Cl2或Pd(PPh3)4。
该发明的有益效果是,同时引入烷基和全氟烷基后,可以显著增加此类材料在有机溶剂中的溶解性,能形成有序结晶或液晶结构,此结构易于载流子的传输,从而得到高的迁移率,同时增强其光热稳定性和在场效应晶体管中的器件稳定性。
附图说明
图1为四个聚合物SCLC在黑暗条件下测试得到的J-V特性曲线,以表1相对应。
具体实施方式
本发明将通过以下实施例作进一步说明。
实施例1。聚合物8CH4CF-1的合成。
在50mL的两口瓶中依次加入1(0.5mmol,204.88mg),8CH4CF-PDI-2Br(0.5mmol,604.30mg),Pd(PPh3)4(0.05mmol,57.78mg),甲苯(10mL),在温度为110℃反应18h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到紫黑色固体聚合物367.6mg,收率67%,即为聚合物8CH4CF-1。数均分子量:13000,分散指数:1.54(THF为流动相,聚苯乙烯为标准)。1H NMR(600MHz,CDCl3)δ8.76(s,2H),8.49(s,4H),7.44(s,2H),5.74(s,2H),3.34(s,2H),2.55(s,2H),2.33(s,2H),1.89(s,2H),1.28(s,16H),0.91(s,6H).19F NMR(565MHz,CDCl3)δ-113.71(s),-114.21(s),-115.02(s),-115.48(s),-124.39(s),-125.90(s)。
实施例2。聚合物6CH4CF-2的合成。
在50mL的两口瓶中依次加入2(0.5mmol,232.92mg),6CH4CF-PDI-2Br(0.5mmol,576.25mg),Pd(PPh3)4(0.05mmol,57.78mg),甲苯(10mL),在温度为110℃反应20h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到紫黑色固体聚合物356.2mg,收率63%,即为聚合物6CH4CF-2。数均分子量:23500,分散指数:2.856(THF为流动相,聚苯乙烯为标准)。1H NMR(400MHz,CDCl3)δ9.30-8.61(m,2H),8.41(d,4H),7.63(d,2H),5.72(s,2H),3.35(s,2H),2.52(d,2H),2.31(s,2H),1.93(d,2H),1.26(s,8H),0.84(s,6H).19F NMR(377MHz,CDCl3)δ-34.23,-81.47,-114.67,-115.54,-124.86,-126.36。
实施例3。聚合物8CH4CF-2的合成。
在50mL的两口瓶中依次加入2(0.4mmol,186.33mg),8CH4CF-PDI-2Br(0.4mmol,483.44mg),Pd(PPh3)4(0.04mmol,46.22mg),甲苯(10mL),在温度为110℃反应20h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到紫黑色固体聚合物308.6mg,收率65%,即为聚合物8CH4CF-2。数均分子量:31000,分散指数:1.62(THF为流动相,聚苯乙烯为标准)。1H NMR(400MHz,CDCl3)δ9.30-8.61(m,2H),8.41(d,4H),7.63(d,2H),5.72(s,2H),3.35(s,2H),2.54(d,2H),2.35(s,2H),1.96(d,2H),1.25(s,16H),0.84(s,6H).19F NMR(377MHz,CDCl3)δ-34.23,-81.47,-114.67,-115.54,-124.86,-126.36。
实施例4。聚合物6CH4CF-3的合成。
在50mL的两口瓶中依次加入3(0.4mmol,196.75mg),6CH4CF-PDI-2Br(0.4mmol,461.00mg),Pd(PPh3)4(0.04mmol,46.22mg),甲苯(10mL),在温度为110℃反应14h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到紫黑色固体聚合物328.6mg,收率71%,即为聚合物6CH4CF-3。数均分子量:62300,分散指数:1.55(THF为流动相,聚苯乙烯为标准)。1H NMR(500MHz,CDCl3)δ8.76(d,2H),8.43-8.37(d,4H),7.33-7.18(d,4H),5.71(s,2H),3.34(s,2H),2.52(s,2H),2.36(s,2H),1.91(s,2H),1.31(d,8H),0.87(s,6H).19F NMR(377MHz,CDCl3)δ34.23,-81.51,-114.70,-115.48,-124.91,-126.38。
实施例5。聚合物8CH4CF-3的合成。
在50mL的两口瓶中依次加入3(0.3mmol,147.6mg),8CH4CF-PDI-2Br(0.3mmol,345.8mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.048mmol,14.6mg),甲苯(10mL),在温度为110℃反应1h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到蓝黑色固体聚合物318.3mg,收率87%,即为聚合物8CH4CF-3。数均分子量:33300,分散指数:1.98(THF为流动相,聚苯乙烯为标准)。1H NMR(400MHz,CDCl3)δ8.76(d,2H),8.43(s,4H),7.33-7.11(m,4H),5.71(s,2H),3.36(s,2H),2.52(s,2H),2.35(s,2H),1.91(s,2H),1.26(s,16H),0.83(s,6H).19F NMR(377MHz,CDCl3)δ-34.23,-81.50,-114.70,-115.46,-124.85,-126.37。
实施例6。聚合物6CH6CF-4的合成。
在50mL的两口瓶中依次加入4(0.3mmol,156.58mg),6CH4CF-PDI-2Br(0.3mmol,405.76mg),Pd(PPh3)4(0.03mmol,34.67mg),甲苯(10mL),在温度为110℃反应21h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到蓝黑色固体聚合物391.3mg,收率70%,即为聚合物6CH4CF-4。数均分子量:35000,分散指数:1.79(THF为流动相,聚苯乙烯为标准)。1H NMR(400MHz,CDCl3)δ9.30-8.61(m,2H),8.41(d,4H),7.63(d,2H),5.72(s,2H),3.12(s,2H),2.50(d,2H),2.35(s,2H),1.96(d,2H),1.25(s,20H),0.84(s,6H).19F NMR(377MHz,CDCl3)δ-113.68(s),-114.21(s),-115.10(s),-115.47(s),-124.35(s),-125.87(s)。
实施例7。聚合物8CH6CF-5的合成。
在50mL的两口瓶中依次加入5(0.3mmol,172.20mg),8CH6CF-PDI-2Br(0.3mmol,422.59mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.030mmol,9.13mg),甲苯(10mL),在温度为110℃反应3h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到蓝黑色固体聚合物345.4mg,收率77%,即为聚合物8CH6CF-5。数均分子量:33000,分散指数:1.62(THF为流动相,聚苯乙烯为标准)。1H NMR(600MHz,CDCl3)δ8.81(s,1H),8.74(s,1H),8.39(d,J=50.5Hz,4H),7.32(s,2H),7.21(s,2H),5.76(s,2H),3.37(s,2H),2.59(s,2H),2.39(s,2H),1.94(s,2H),1.29(s,16H),0.86(s,6H);19F NMR(565MHz,CDCl3)δ-113.78(s),-114.19(s),-115.07(s),-115.52(s),-124.37(s),-125.89(s)。
实施例8。聚合物8CH4CF-6的合成。
在50mL的两口瓶中依次加入6(0.3mmol,231.70mg),8CH4CF-PDI-2Br(0.3mmol,362.58mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.048mmol,14.6mg),甲苯(10mL),在温度为110℃反应1.5h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到蓝黑色固体聚合物367.4mg,收率82%,即为聚合物8CH4CF-6。数均分子量:16000,分散指数:1.78(THF为流动相,聚苯乙烯为标准)。1H NMR(400MHz,CDCl3)δ8.83(d,2H),8.49(s,2H),8.01(s,2H),7.10(s,2H),5.69(s,2H),3.45(s,2H),2.84(s,4H),2.51(s,2H),1.26(s,38H),0.84(s,18H).19F NMR(377MHz,CDCl3)δ-34.21,-81.25,-123.24,-126.63。
实施例9。聚合物6CH4CF-7的合成。
在50mL的两口瓶中依次加入7(0.3mmol,271.4mg),6CH4CF-PDI-2Br(0.3mmol,345.75mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.048mmol,14.6mg),甲苯(10mL),在温度为110℃反应10h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到紫黑色固体聚合物413mg,收率88%,即为聚合物6CH4CF-7。数均分子量:75677,分散指数:1.95(THF为流动相,聚苯乙烯为标准)。1H NMR(500MHz,CDCl3)δ8.83(d,2H),8.64–8.11(m,2H),7.96(d,2H),6.79(s,2H),5.71(s,2H),3.33(s,2H),2.76(s,4H),2.58(s,2H),2.33(s,2H),1.92(s,2H),1.26(s,30H),0.83(s,18H).19F NMR(377MHz,CDCl3)δ-34.23,-81.48,-124.91,-126.35。
实施例10。聚合物8CH4CF-7的合成。
在50mL的两口瓶中依次加入7(0.3mmol,271.4mg),8CH4CF-PDI-2Br(0.3mmol,362.6mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.048mmol,14.6mg),甲苯(10mL),在温度为110℃反应10h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到蓝黑色固体聚合物444.2mg,收率91%,即为聚合物8CH4CF-7。数均分子量:60729,分散指数:1.87(THF为流动相,聚苯乙烯为标准)。1H NMR(400MHz,CDCl3)δ8.83(d,2H),8.49(s,2H),8.01(s,2H),6.80(s,2H),5.69(s,2H),3.33(s,2H),2.76(s,4H),2.51(s,2H),2.32(s,2H),1.91(s,2H),1.26(s,38H),0.84(s,18H).19F NMR(377MHz,CDCl3)δ-34.23,-81.27,-123.28,-126.66。
实施例11。聚合物8CH6CF-7的合成。
在50mL的两口瓶中依次加入7(0.3mmol,271.4mg),8CH4CF-PDI-2Br(0.3mmol,422.59mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.048mmol,14.6mg),甲苯(10mL),在温度为110℃反应10h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到蓝黑色固体聚合物471.1mg,收率86%,即为聚合物8CH4CF-7。数均分子量:38818,分散指数:1.66(THF为流动相,聚苯乙烯为标准)。1H NMR(500MHz,CDCl3)δ8.83(d,2H),8.52(s,2H),8.06(s,2H),6.79(s,2H),5.70(s,2H),3.33(s,2H),2.74(s,4H),2.51(s,2H),2.31(s,2H),1.88(s,2H),1.23(s,38H),0.80(s,18H).19F NMR(377MHz,CDCl3)δ-34.23,-81.24,-122.23,-123.25,-123.94,-126.60。
实施例12。聚合物6CH6CF-7的合成。
在50mL的两口瓶中依次加入7(0.3mmol,271.4mg),6CF6CH-PDI-2Br(0.3mmol,405.7mg),Pd2(dba)3(0.006mmol,5.5mg),P(o-Tol)3(0.048mmol,14.6mg),甲苯(10mL),在真空的条件下,保持温度为110℃反应10h,趁热将反应混合物加入甲醇中,搅拌,加完之后沉降0.5h,抽滤,干燥,过柱,旋蒸,得到紫黑色固体聚合物491mg,收率90%,即为聚合物6CH6CF-BDT。数均分子量:72715,分散指数:1.90(THF为流动相,聚苯乙烯为标准)。1H NMR(500MHz,CDCl3)δ8.89(s,2H),8.49(s,2H),8.03(s,2H),6.82(s,2H),5.70(s,2H),3.33(s,2H),2.74(s,4H),2.62(s,2H),2.36(s,2H),1.97(d,2H),1.25(s,30H),0.87(s,18H).19FNMR(377MHz,CDCl3)δ-34.17,-81.29,-106.56,-122.36,-123.28,-126.63。
上述制备的聚合物中,对其中的8CH4CF-3,6CH4CF-3,8CH6CF-5,8CH4CF-7采用了空间电荷限制电流(SCLC)的方法测量纯膜的电子迁移率,以了解在光伏性能中电荷传输的性能。表1可以看出,3个聚合物的电子迁移率都在10-3级别,8CH6CF-5的迁移率在7.2x 10-4是由于制备器件时所涂的活性层材料只有84nm厚,经过公式(1)计算得到的迁移率数值相对其他3个较低。
表1
聚合物 | 膜厚/nm | 电子迁移率/cm2·V–1·s–1 |
8CH4CF-3 | 181 | 8.4x 10-3 |
6CH4CF-3 | 110 | 1.3x 10-3 |
8CH6CF-5 | 84 | 7.2x 10-4 |
8CH4CF-7 | 151 | 1.6x 10-3 |
图1为四个聚合物SCLC在黑暗条件下测试得到的J-V特性曲线,以表1相对应。因此,本发明得到的一类全氟烷基修饰的苝酰亚胺共轭聚合物具有高迁移率性能,可用于场效应晶体管和有机聚合物太阳能电池的活性层材料。
Claims (2)
1.一类全氟烷基修饰的苝酰亚胺共轭聚合物,其特征是结构通式为:
R为全氟烷基链,结构式如下:
其中:m、n分别是烷基C原子的个数和全氟烷基C原子的个数,m是1、2、3、4、5、6,n是1、3、5、7;
Ar为噻吩,结构式如下:
并二噻吩:
联二噻吩:
并三噻吩:
联三噻吩:
BDT单元:
PBDTT单元:
IDT单元:
2.权利要求1所述的一类全氟烷基修饰的苝酰亚胺共轭聚合物及其合成方法,其特征是按如下步骤:
以1,7-二溴全氟烷基苝酰亚胺与双锡试剂为原料,摩尔比为1:1,按溶剂与原料摩尔比300~400:1的量、催化剂与原料摩尔比0.02~0.1:1的量,加入溶剂和催化剂,无水无氧和溶剂的回流温度条件下,进行stille偶联反应,生成全氟烷基修饰的苝酰亚胺共轭聚合物;
所述的双锡试剂为噻吩双锡、并二噻吩双锡、联二噻吩双锡、并三噻吩双锡、联三噻吩双锡、BDT双锡、PBDTT双锡或IDT双锡;
所述的溶剂为氯苯、甲苯、三氟甲苯或DMF;
所述的催化剂为Pd2(dba)3/P(o-tol)3、Pd(PPh3)2Cl2或Pd(PPh3)4。
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