CN111944127A - 一种基于苝酰亚胺共轭平面扩展的d-a聚合物及其制备方法 - Google Patents
一种基于苝酰亚胺共轭平面扩展的d-a聚合物及其制备方法 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及材料合成和有机半导体技术领域,尤其是一种基于苝酰亚胺共轭平面扩展的D-A聚合物及其制备方法。
背景技术
近年来,共轭聚合物研究工作方兴未艾,逐渐形成了包括共轭聚合物设计与合成、共轭聚合物光电功能材料构效关系及相应器件物理研究在内的一个集化学、物理学、材料学、信息科学等多学科交叉的研究领域。与传统无机半导体材料相比,共轭聚合物具有更有效的性能调节性,通过改变聚合物主链和侧链取代基可以很方便地调节聚合物的溶解性能、光学性能、电化学性能及结晶、组装性能等。另外,共轭聚合物材料具有非常优异的成膜加工性能,可以通过旋涂、丝网印刷、喷墨打印等方式,制成大面积、轻质、柔性器件,彰显出其独特的魅力。
苝-3,4:9,10-四羧酸二酰亚胺类化合物即苝酰亚胺(PDI),具有较高的电子迁移率和电子亲和力、在可见光区具有很强的吸光能力、易调节的能级、低的合成成本,而广泛应用于有机半导体技术领域。异靛蓝分子不仅具有缺电子的作用成为D-A型分子的核心骨架,另外可以通过一系列对结构的修饰来调节异靛蓝的分子能级(最高已占分子轨道 -HOMO和最低分子未占轨道-LUMO),从而使异靛蓝分子成为一个理想的吸电子骨架基团。但现有的发现中,还未将这两种构筑单元融合起来进行***的研究。
因此,通过一种简单、绿色的方法合成出一种新的苝酰亚胺融合异靛蓝单体,对合成 D-A聚合物的发展具有重要的意义。
发明内容
本发明的目的之一在于提供一种新型的、稳定的、溶解性好的基于苝酰亚胺共轭平面扩展的D-A聚合物,该聚合物有效提高了有机半导体的器件性能。
为解决上述技术问题,本发明提供的技术方案是这样的:一种基于苝酰亚胺共轭平面扩展的D-A聚合物,该聚合物的结构通式如式(I)所示:
式中R,R’为C5~C18的叉链或者直链,n为1~100的正整数;所述基于苝酰亚胺共轭平面扩展的D-A聚合物,R或R’为以下基团中的一种(n,m为正整数):
Ar为以下基团中的一种:
Ar’为以下基团中的一种:
所述聚合物的分子结构如下任一所示:
本发明还提供了另一种基于苝酰亚胺共轭平面扩展的D-A聚合物,该聚合物的结构通式如式(II)所示:
式中R,R’为C5~C18的叉链或者直链,n为1~100的正整数;所述基于苝酰亚胺共轭平面扩展的D-A聚合物,R或R’为以下基团中的一种:
所述聚合物的分子结构为:
本发明的目的之二在于提供上述基于苝酰亚胺共轭平面扩展的D-A聚合物(I)的制备方法,包括以下步骤:
步骤S1:在惰性气体保护下,向含催化剂存在的四氢呋喃中加入1,7-二溴苝酰亚胺和 6-硼酯靛红,于80℃下进行Suzuki偶联反应,后光催化关环反应,纯化后得到化合物a1;
步骤S2:在惰性气体的保护下,向反应容器中加入化合物a1、6-溴吲哚二酮,在乙酸中进行反应,纯化后得到化合物b1;
步骤S3:在惰性气体的保护下,向反应容器中加入化合物b1、含Ar的锡试剂,在含有催化剂的溶剂中,于110℃~120℃进行12~36小时的Still聚合反应,纯化后得到(I)类聚合物。
更进一步地,步骤S1所述1,7-二溴苝酰亚胺和6-硼酯靛红的摩尔比为1:2~1:2.5;所述光照为450nm蓝光;所述的催化剂为摩尔比为1:3~1:4的二(三苯基膦)二氯化钯和三(邻甲基苯基)膦或三(二亚苄基丙酮)二钯和三叔丁基膦四氟硼酸盐的混合物,催化剂的摩尔比用量比为反应物A的10%~12%;
更进一步地,步骤S2所述所述化合物a1、6-溴吲哚二酮的摩尔比为1:1~1:3;反应温度为110~120℃,反应时间为12~24小时;
更进一步地,步骤S3所述所述化合物b1和含Ar的锡试剂的摩尔比为1:1~1:1.2;所述含Ar的锡试剂为三甲基锡噻吩、三甲基锡联噻吩、三甲基锡双氟联噻吩;所述催化剂为摩尔比为1:3~1:4的三(二亚苄基丙酮)二钯和三(邻甲基苯基)膦的混合物;所述溶剂为四氢呋喃、二氧六环、N,N-二甲基二酰胺、甲苯中的至少一种;所述反应温度为110℃~120℃,反应时间为12~36小时。
一种如上所述基于苝酰亚胺共轭平面扩展的D-A聚合物式(II)的制备方法,包括以下步骤:
步骤S4:在惰性气体的保护下,向反应容器中加入苝酰亚胺二溴化产物、2,7-三甲基锡对称引达省并二噻吩衍生物,在含有催化剂的溶剂中,于110℃~120℃进行12~36小时的Still聚合反应,后关环反应,纯化后得到(II)类聚合物;
更进一步地,步骤S4所述溶剂为四氢呋喃、二氧六环、N,N-二甲基二酰胺、甲苯中的至少一种;所述苝酰亚胺二溴化产物、2,7-三甲基锡对称引达省并二噻吩衍生物的摩尔比为1:1~1:1.2;所述催化剂为摩尔比为1:3~1:4的三(二亚苄基丙酮)二钯和三(邻甲基苯基)膦的混合物;催化剂的摩尔比用量比为反应物A的10%~12%;反应温度为110℃~120℃,反应时间为12~36小时。
具体地,所述步骤S1为:将1,7-二溴苝酰亚胺和6-硼酯靛红称量加入到反应封管瓶中,脱气换高纯氮气,连续三次;鼓气状态加入催化剂,使催化剂的用量比为反应物A的10%~12%,然后加入甲苯溶剂搅拌,使反应物A的摩尔浓度为0.3-0.6mol.L之间,随后升温至80℃反应12小时,反应完恢复室温,先萃取,然后经过层析柱纯化;将得到的粗产物,称量加入到柱形反应瓶,加入碘单质作为催化剂,然后加入甲苯溶剂,使反应物的摩尔浓度为0.001-0.003mol.L之间,80℃-90℃加热,在空气的气氛下,LED蓝光持续照射 12~24小时,反应完后恢复室温,将反应溶液减压蒸馏,然后层析柱分离纯化,得到产物a1;
具体地,所述步骤S2为:将S1制备的产物a1,6-溴吲哚二酮按照1:2~1:3的摩尔比加入到两口反应瓶中,然后脱气换高纯氮气,重复操作三次,随后在氮气环境下,注射器注入盐酸,溶剂乙酸,使反应物的摩尔浓度为0.1-0.3mol.L之间,随后升温至110℃~120℃之间,加热搅拌,反应12~24小时,反应完后恢复至室温,先萃取后旋转蒸发溶剂,最后层析柱分离纯化,得到产物b1;
具体地,所述步骤S3为:将聚合单体b1和三甲基锡噻吩、三甲基锡联噻吩、三甲基锡双氟联噻吩分别按照摩尔比1:1称量于聚合反应瓶中,脱气换高纯氮气,重复操作三次,鼓气状态下按次序加入催化剂为摩尔比为1:3~1:4的三(二亚苄基丙酮)二钯和三(邻甲基苯基)膦的混合物,催化剂的摩尔比用量比为反应物A的10%~12%,加入无水甲苯溶剂,使反应物的摩尔浓度为0.01-0.02mol.L之间,抽充换气15~20次,保证完全无水无氧的反应环境,110℃~120℃加热搅拌,反应12~36小时;反应后恢复至室温,加入甲苯溶剂加热搅拌至溶解,再恢复至室温,滴加到甲醇溶液中搅拌沉降至少30分钟,将混合液倒入纤维滤筒中过滤;将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物1、2、3;
具体地,所述步骤S4为:将苝酰亚胺双溴化产物和2,7-三甲基锡对称引达省并二噻吩衍生物按照摩尔比1:1称量于聚合反应瓶中,脱气换高纯氮气,重复操作三次,鼓气状态下按次序加入催化剂为摩尔比为1:3~1:4的三(二亚苄基丙酮)二钯和三(邻甲基苯基)膦的混合物,催化剂的摩尔比用量比为反应物A的10%~12%,加入无水甲苯溶剂,使反应物的摩尔浓度为0.01-0.02mol.L之间,抽充换气15~20次,保证完全无水无氧的反应环境,110℃~120℃加热搅拌,反应12~36小时;反应后恢复至室温,加入甲苯溶剂加热搅拌至溶解,再恢复至室温,滴加到甲醇溶液中搅拌沉降至少30分钟,将混合液倒入纤维滤筒中过滤;将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物4未关环前体;将该聚合物加入到圆底烧瓶中,加入甲苯溶剂,使反应物浓度为0.001-0.003mol/L之间,缓慢滴加无水三氯化铁和硝基甲烷的混合液,催化剂的摩尔比用量比为反应物的1:5~1:10之间, 60℃~80℃加热搅拌,12~24小时,反应后恢复室温,先萃取后索氏提取,沉降,干燥得聚合物4;
本发明与现有技术相比,具有以下优点:
(1)本发明通过一种简单,绿色的方法合成出一种新颖的苝酰亚胺融合异靛蓝单体,该结构含有酰亚胺和酰胺键,具有更低的最低未占分子轨道,更高的电子亲合能,是良好的电子受体单元。
(2)该聚合单体与富电子基团的噻吩类单体聚合,得到一系列的D-A聚合物。该聚合物溶解性良好、产率高、热稳定性高有利于大面积器件的制备。
(3)与常规的聚合物相比具有更大的共轭结构,更加有利于电子的传输,并且最大吸收波长在可见光领域,光学带隙窄,在有机场效应晶体管(OFET)、有机太阳能电池(OPV)领域具有潜在的应用前景。
附图说明
图1为苝酰亚胺共轭平面扩展的D-A聚合物的制备化学反应方程式;
图2为实施例1中化合物b1的1H NMR谱图;
图3为实施例1中聚合物1的1H NMR谱图;
图4为实施例1中聚合物1的循环伏安曲线;
图5为实施例1中聚合物2的紫外吸收曲线;
图6为实施例1中聚合物2的循环伏安曲线;
图7为实施例1中聚合物3的紫外吸收曲线;
图8为实施例1中聚合物3的循环伏安曲线;
图9为实施例1中聚合物4的紫外吸收曲线。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
本发明采用瑞士Bruker公司生产的AVANCE III 400M型液体核磁共振谱仪来检测产物得1H NMR、谱图,溶剂为氘代氯仿(CDCl3),四甲基硅烷(TMS)为内标。本实验采用Shimadzu公司的UV-3600型紫外可见分光光度计来测定产物的紫外吸收光谱,采用 1×1cm的石英比色皿作为样品池,采用上海辰华仪器有限公司的CHI620E电化学分析仪。采用华太科思(WATTCAS)有限公司的高温光平行反应仪WP-TEC-1020HSL来做光催化关环反应。
本发明下述具体实施方式中的苝酰亚胺共轭平面扩展的D-A聚合物制备过程中的化学反应方程式如图1所示。
实施例1
(1)将0.76g的2-癸基十四烷-1-胺取代的1,7-二溴苝酰亚胺(DT-PDI)和0.84g 1-溴-2-癸基十四烷取代的6-硼酯靛红加入到封管瓶中,脱气换气,连续三次;然后加入20ML的四氢呋喃溶剂和1.5ML(2mol.L)的磷酸三钾水溶液搅拌,鼓气状态加入17.2mg的三(二亚苄基丙酮)二钯催化剂和21.8mg的三叔丁基膦四氟硼酸盐,抽充换气三次,随后升温至80℃反应12小时,反应完恢复室温,先萃取,然后经过层析柱纯化,洗脱剂比例二氯甲烷和石油醚的比例为3:5;将得到的粗产物,称量50mg加入到柱形反应瓶,加入一粒碘单质作为催化剂,然后加入20ML甲苯溶剂,90℃加热,在空气的气氛下,LED 蓝光持续照射12小时,反应完后恢复室温,将反应溶液减压蒸馏,然后层析柱分离纯化,洗脱剂比例二氯甲烷和石油醚的比例为1:1,得到产物a1;
(2)将350mg的a1和309mg的6-溴-1-(2-癸基十四烷基)吲哚-2-酮加入到双口圆底反应瓶中,抽充换气重复操作三次,在氮气的环境下,鼓气加入16.5mg的一水合.对甲苯磺酸和17.2mg的五氧化二磷,随后注射10ML的无水甲苯溶剂,115℃加热搅拌反应 48小时;恢复至室温,先萃取后溶液减压蒸馏,然后层析柱分离纯化,洗脱剂比例二氯甲烷和石油醚的比例为2:3,得到产物b1;
(3)将54mg的b1和7.17mg的2,5-三甲基锡噻吩加入到聚合瓶中,抽充换气,重复操作三次,鼓气加入1.5ML的无水无氧甲苯溶剂,随后加入1.81mg的三(二亚苄基丙酮)二钯催化剂和2.41mg的三(邻甲基苯基)膦配体,抽充换气15-20次,110℃加热搅拌36小时;反应完后恢复室温,加入2ML甲苯溶剂升温至120℃溶解后再恢复至室温,滴加到甲醇溶液中搅拌沉降至少30分钟,将混合液倒入纤维滤筒中过滤;将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物1;
实施例2
(1)将0.76g的2-癸基十四烷-1-胺取代的1,7-二溴苝酰亚胺(DT-PDI)和0.84g 1-溴-2-癸基十四烷取代的6-硼酯靛红加入到封管瓶中,脱气换气,连续三次;然后加入20ML的四氢呋喃溶剂和1.5ML(2mol.L)的磷酸三钾水溶液搅拌,鼓气状态加入17.2mg的三(二亚苄基丙酮)二钯催化剂和21.8mg的三叔丁基膦四氟硼酸盐,抽充换气三次,随后升温至80℃反应12小时,反应完恢复室温,先萃取,然后经过层析柱纯化,洗脱剂比例二氯甲烷和石油醚的比例为3:5;将得到的粗产物,称量50mg加入到柱形反应瓶,加入一粒碘单质作为催化剂,然后加入20ML甲苯溶剂,90℃加热,在空气的气氛下,LED 蓝光持续照射12小时,反应完后恢复室温,将反应溶液减压蒸馏,然后层析柱分离纯化,洗脱剂比例二氯甲烷和石油醚的比例为1:1,得到产物a1;
(2)将350mg的a1和309mg的6-溴-1-(2-癸基十四烷基)吲哚-2-酮加入到双口圆底反应瓶中,抽充换气重复操作三次,在氮气的环境下,鼓气加入16.5mg的一水合.对甲苯磺酸和17.2mg的五氧化二磷,随后注射10ML的无水甲苯溶剂,115℃加热搅拌反应 48小时;恢复至室温,先萃取后溶液减压蒸馏,然后层析柱分离纯化,洗脱剂比例二氯甲烷和石油醚的比例为2:3,得到产物b1;
(3)将63.16mg的b1和10.07mg的5,5'-双(三甲基锡基)-2,2'-二噻吩加入到聚合瓶中,抽充换气,重复操作三次,鼓气加入1.5ML的无水无氧甲苯溶剂,随后加入1.55mg 的三(二亚苄基丙酮)二钯催化剂和2.06mg的三(邻甲基苯基)膦配体,抽充换气15-20 次,110℃加热搅拌36小时;反应完后恢复室温,加入2ML甲苯溶剂升温至120℃溶解后再恢复至室温,滴加到甲醇溶液中搅拌沉降至少30分钟,将混合液倒入纤维滤筒中过滤;将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物2;
实施例3
(1)将0.76g的2-癸基十四烷-1-胺取代的1,7-二溴苝酰亚胺(DT-PDI)和0.84g 1-溴-2-癸基十四烷取代的6-硼酯靛红加入到封管瓶中,脱气换气,连续三次;然后加入20ML的四氢呋喃溶剂和1.5ML(2mol.L)的磷酸三钾水溶液搅拌,鼓气状态加入17.2mg的三(二亚苄基丙酮)二钯催化剂和21.8mg的三叔丁基膦四氟硼酸盐,抽充换气三次,随后升温至80℃反应12小时,反应完恢复室温,先萃取,然后经过层析柱纯化,洗脱剂比例二氯甲烷和石油醚的比例为3:5;将得到的粗产物,称量50mg加入到柱形反应瓶,加入一粒碘单质作为催化剂,然后加入20ML甲苯溶剂,90℃加热,在空气的气氛下,LED 蓝光持续照射12小时,反应完后恢复室温,将反应溶液减压蒸馏,然后层析柱分离纯化,洗脱剂比例二氯甲烷和石油醚的比例为1:1,得到产物a1;
(2)将350mg的a1和309mg的6-溴-1-(2-癸基十四烷基)吲哚-2-酮加入到双口圆底反应瓶中,抽充换气重复操作三次,在氮气的环境下,鼓气加入16.5mg的一水合.对甲苯磺酸和17.2mg的五氧化二磷,随后注射10ML的无水甲苯溶剂,115℃加热搅拌反应 48小时;恢复至室温,先萃取后溶液减压蒸馏,然后层析柱分离纯化,洗脱剂比例二氯甲烷和石油醚的比例为2:3,得到产物b1;
(3)将43.24mg的b1和7.4mg的(3,3'-二氟-[2,2'-二噻吩]-5,5'-二基)双(三甲基锡)加入到聚合瓶中,抽充换气,重复操作三次,鼓气加入1.0ML的无水无氧甲苯溶剂,随后加入2.47mg的三(二亚苄基丙酮)二钯催化剂和3.28mg的三(邻甲基苯基)膦配体,抽充换气15-20次,110℃加热搅拌36小时;反应完后恢复室温,加入2ML甲苯溶剂升温至120℃溶解后再恢复至室温,滴加到甲醇溶液中搅拌沉降至少30分钟,将混合液倒入纤维滤筒中过滤;将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物3;
实施例4
(1)将80.66mg的十一碳六胺取代的二溴苝酰亚胺(1,7位取代和1,6位取代的二溴的异构体,二者比例大约为4:1)和116.08mg的2,7-三甲基锡对称引达省并二噻吩衍生物加入到聚合瓶中,抽充换气,重复操作三次,鼓气加入2.0ML的无水无氧甲苯溶剂,随后加入2.59mg的三(二亚苄基丙酮)二钯催化剂和3.44mg的三(邻甲基苯基)膦配体,抽充换气15-20次,110℃加热搅拌36小时;反应完后恢复室温,加入2ML甲苯溶剂升温至120℃溶解后再恢复至室温,滴加到甲醇溶液中搅拌沉降至少30分钟,将混合液倒入纤维滤筒中过滤;将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物4的前体;
(2)将60mg的聚合物4的前体加入单口圆底反应瓶中,加入80ML的无水甲苯溶剂,滴加2ML硝基甲烷和50mg无水三氯化铁的混合溶液,并持续向反应体系中鼓氮气, 65℃加热搅拌反应48小时;恢复至室温,先萃取后旋转蒸发溶剂,后溶解沉降,将过滤后的纤维滤筒放入索氏提取器中,甲醇、丙酮、正己烷、二氯甲烷、氯仿依次提取;甲醇沉降,抽滤,真空干燥箱加热烘干得纯净聚合物4;
Claims (12)
7.一种如权利要求1所述基于苝酰亚胺共轭平面扩展的D-A聚合物的制备方法,其特征在于,包括以下步骤:
步骤S1:在惰性气体保护下,向含催化剂存在的四氢呋喃中加入1,7-二溴苝酰亚胺和6-硼酯靛红,于80℃下进行Suzuki偶联反应,后光催化关环反应,纯化后得到化合物a1;
步骤S2:在惰性气体的保护下,向反应容器中加入化合物a1、6-溴吲哚二酮,在乙酸中进行反应,纯化后得到化合物b1;
步骤S3:在惰性气体的保护下,向反应容器中加入化合物b1、含Ar的锡试剂,在含有催化剂的溶剂中,于110℃~120℃进行12~36小时的Still聚合反应,纯化后得到(I)类聚合物。
8.根据权利要求5所述基于苝酰亚胺共轭平面扩展的D-A聚合物的制备方法,其特征在于,步骤S1所述1,7-二溴苝酰亚胺和6-硼酯靛红的摩尔比为1:2~1:2.5;所述光照为450nm蓝光;所述的催化剂为摩尔比为1:3~1:4的二(三苯基膦)二氯化钯和三(邻甲基苯基)膦或三(二亚苄基丙酮)二钯和三叔丁基膦四氟硼酸盐的混合物,催化剂的摩尔比用量比为反应物A的10%~12%。
9.根据权利要求5所述基于苝酰亚胺共轭平面扩展的D-A聚合物的制备方法,其特征在于,步骤S2所述所述化合物a1、6-溴吲哚二酮的摩尔比为1:1~1:3;反应温度为110℃~120℃,反应时间为12~24小时。
10.根据权利要求5所述基于苝酰亚胺共轭平面扩展的D-A聚合物的制备方法,其特征在于,步骤S3所述所述化合物b1和含Ar的锡试剂的摩尔比为1:1~1:1.2;所述含Ar的锡试剂为三甲基锡噻吩、三甲基锡联噻吩、三甲基锡双氟联噻吩;所述催化剂为摩尔比为1:3~1:4的三(二亚苄基丙酮)二钯和三(邻甲基苯基)膦的混合物;所述溶剂为四氢呋喃、二氧六环、N,N-二甲基二酰胺、甲苯中的至少一种;所述反应温度为110℃~120℃,反应时间为12~36小时。
11.一种如权利要求3所述基于苝酰亚胺共轭平面扩展的D-A聚合物的制备方法,其特征在于,包括以下步骤:
步骤S4:在惰性气体的保护下,向反应容器中加入苝酰亚胺二溴化产物、2,7-三甲基锡对称引达省并二噻吩衍生物,在含有催化剂的溶剂中,于110℃~120℃进行12~36小时的Still聚合反应,后关环反应,纯化后得到(II)类聚合物。
12.根据权利要求8所述基于苝酰亚胺共轭平面扩展的D-A聚合物的制备方法,其特征在于,步骤S4所述溶剂为四氢呋喃、二氧六环、N,N-二甲基二酰胺、甲苯中的至少一种;所述苝酰亚胺二溴化产物、2,7-三甲基锡对称引达省并二噻吩衍生物的摩尔比为1:1~1:1.2;所述催化剂为摩尔比为1:3~1:4的三(二亚苄基丙酮)二钯和三(邻甲基苯基)膦的混合物;催化剂的摩尔比用量比为反应物A的10%~12%;反应温度为110℃~120℃,反应时间为12~36小时。
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