CN104341584A - 聚3,8-二吲哚并吡咯及其制备方法和应用 - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
本发明公开了一种聚3,8-二吲哚并吡咯及其制备方法和应用，其结构如下：其中，R1是C6～C20的烷基链；R2为C6～C20的烷基链或芳香基团，n为≥1的整数。其制备方法为将二(2-硝基-4-溴苯)吡咯衍生物和亚磷酸三乙酯或者三苯基膦反应，得到3,8-二溴吲哚并吡咯衍生物；在3,8-二溴吲哚并吡咯衍生物上接上烷基后，通过Miyaura反应再将3,8-二溴吲哚并吡咯转化为相应的硼酸酯，将3,8-二溴吲哚并吡咯和它的硼酸酯进行聚合反应，得到聚3,8-二溴吲哚并吡咯。本发明工艺可靠，合成步骤少。该聚合物具有可溶性，因而适合旋涂或者打印成膜，从而在电致发光、光伏电池、非线性光学和传感领域得到应用。
Description
技术领域
本发明属于新型功能高分子材料，尤其是一种可溶性聚3,8-二吲哚并吡咯，可广泛用于电致发光、光伏电池、薄膜场效应晶体管、记忆材料和传感领域。
背景技术
自1977年日本科学家白川英树发现聚乙炔导电以来，这种被称为“第四代高分子材料”的导电聚合物以其突出的光电性能吸引了众多科学家进行研究。与具有相同或相近用途的无机材料相比，导电高分子具有轻质、易加工等优点。由于这类材料结构的共轭特性，使它能传输电荷、受激发光、从而能够或可能在许多电子或光电子器件上得到应用，如高分子发光二极管、光伏电池、场效应管等。潜在的应用前景和广泛的应用领域促使科学家竞相研究这类具有光电活性的共轭材料，如聚乙炔、聚吡咯、聚噻吩、聚苯胺、聚苯撑乙烯、聚芴等。
发明内容
本发明的目的在于提一种富含空穴传输基团的聚3,8-二吲哚并吡咯。该聚合物因为芳基上有长链的取代基团而可溶于各种溶剂，适合旋涂或者打印成膜，从而在光伏电池、非线性光学和传感领域得到应用。
同时，本发明还提供上述聚3,8-二吲哚并吡咯的合成方法。
本发明的目的通过以下技术方案实现：
聚3,8-二吲哚并吡咯，具有如下结构：
其中，R1是C6～C20的烷基链；R2为C6～C20的烷基链或芳香基团，R1和R2的作用是促进聚合物的溶解；n为≥1的整数。
所述R1为下列结构中的一种：
C6H13、C8H17、C10H21、C12H25、C16H33。
所述R1为下列结构中的一种：
当R2为烷基链时，例举结构同R1；当R2为芳香基团时，所述R2为下列结构中的一种：
其中，R为C0～C20的烷基或者烷氧基。
所述R为CH3、C2H7、C4H9、C6H13、C6H13O、C8H17O、C10H21O、C12H25O、 C16H33O或C20H41O。
所述R为下列结构中的一种：
所述聚3,8-二吲哚并吡咯的制备方法：将二(2-硝基-4-溴苯)吡咯和亚磷酸三乙酯反应，得到3,8-二溴5,6-烷基11-烷基/芳基二吲哚并吡咯；通过Miyaura反应再将3,8-二溴5,6-烷基11-烷基/芳基二吲哚并吡咯转化为相应的硼酸酯，将3,8-二溴5,6-烷基11-烷基/芳基二吲哚并吡咯和它的硼酸酯进行聚合反应，得到聚3,8-二溴5,6-烷基11-烷基/芳基二吲哚并吡咯。
所述聚3,8-二吲哚并吡咯通过Suzuki或者Yamamoto方法聚合。
聚3,8-二吲哚并吡咯的单体含有三个吡咯基团和两个苯环，五个芳基并成大共轭共平面结构。1.该聚合物有利于空穴注入和传输，氧化电位低于0.4V。 2.分子链之间容易发生聚集，其单体已经发生了明显聚集。3.聚3,8-二吲哚并吡咯比聚芴类、聚硅芴类和聚咔唑类聚合物带隙窄，可以吸收更多可见光。以上特点使得聚3,8-二吲哚并吡咯成为新型的太阳能电池材料、薄膜场效应晶体管材料、记忆材料和传感材料。
本发明的优点有：
(1)材料合成的原料来源广泛，工艺可靠。
(2)本发明的聚3,8-二吲哚并吡咯具有可溶性，因而适合旋涂或者打印成膜，从而在电致发光、光伏电池、非线性光学、薄膜场效应晶体管和传感领域得到应用。
附图说明
图1为2,5-二(2-硝基-4-溴苯)-1-辛基吡咯的核磁氢谱。
图2为3,8-二溴-11-正辛基二吲哚并吡咯核磁氢谱。
图3为3,8-二溴-5,6,11-三正辛基二吲哚并吡咯核磁氢谱。
图4为3,8-二嚬呐醇硼酸酯-5,6,11-三正辛基二吲哚并吡咯核磁氢谱。
图5为2,5-二(2-硝基-4-溴苯)-1-甲苯基吡咯的核磁氢谱。
图6为3,8-二溴-5,6-二氢-9-甲苯基二吲哚并吡咯的核磁氢谱。
图7为3,8-二溴-5,6-二正辛基-9-甲苯基二吲哚并吡咯的核磁碳谱。
图8为3,8-二嚬呐醇硼酸酯-5,6--二正辛基-9-甲苯基二吲哚并吡咯的核磁碳谱。
具体实施方式
下面结合具体实施例对本发明作进一步具体详细描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。
实施例1
(1)3,8-二溴-5,6-二氢-9-辛基二吲哚并吡咯的合成
合成路线如下：
100毫升单口瓶中加入4.7克(8mmol)二(2-硝基-4-溴苯)辛基吡咯，50毫 升亚磷酸三乙酯，换氩气三次，160摄氏度反应5小时。反应结束后减压蒸馏除去过量的亚磷酸三乙酯，用硅胶过柱，得到1.8克3,8-二溴-5,6-二氢-9-辛基二吲哚并吡咯，产率43％。1H NMR(400 MHz,DMSO,ppm):10.886(s,2H),7.686(d,J＝8.4,2H),7.575(s,2H),7.136(d,J＝8.4,2H),4.539(m,2H),1.804(m,2H),1.35～1.0(m,10H),0.719(t,3H).
(2)3,8-二溴-5,6-二正辛基-9-辛基二吲哚并吡咯的合成
合成路线如下：
取1.796克(3.5mmol)3,8-二溴-5,6-二氢-9-辛基二吲哚并吡咯，1.176克(10.5mmol)特丁醇钾，换氩气三次，注入THF 100毫升，80℃加热搅拌回流至澄清，冷却，注入2.702克C8H17Br(14mmol)C8H17Br，回流过夜。冷却加水，加乙酸乙酯萃取，硫酸镁干燥。过滤，旋除溶剂，得到粗产物。用硅胶过柱，得到1.968克3,8-二溴-5,6,9-三辛基二吲哚并吡咯，产率76％。1H NMR(400 MHz,o-dichlorobenzene,ppm):7.880(d,J＝8.4,2H),7.807(s,2H),7.542(d,J＝8.4,2H),4.748(m,2H),4.505(m,4H),2.224(m,2H),2.057(m,4H),1.65～1.25(m,30H),1.107(t,6H),1.034(t,3H).
(3)3,8-二嚬呐醇硼酸酯-5,6,9-三辛基二吲哚并吡咯的合成
合成路线如下：
取0.370克(0.5mmol)3,8-二溴-5,6,9-三辛基二吲哚并吡咯，0.762克(3.0mmol)联二嚬呐醇硼酸酯，0294克(3.0mmol)醋酸钾，22毫克，0.03mmol，1,1'-二(二苯膦基)二茂铁二氯化钯(II)(PdCl2(dppf))，换氩气三次，注入无水 二氧六环15毫升，80摄氏度反应24小时。冷却，旋除二氧六环，加水和二氯甲烷分层，有机层加硫酸镁干燥。过滤，旋除溶剂，将粗产物过柱得到224毫克3,8-二嚬呐醇硼酸酯-5,6,9-三辛基二吲哚并吡咯，产率54％。
(4)聚5,6-二正辛基-9-甲苯基二吲哚并吡咯3,8-基的合成
合成路线如下：
取0.28毫克醋酸钯(PdOAc2)、1.83毫克三(邻甲苯基)膦(P(o-Toly)3)、0.145克(0.197mmol)3,8-二溴-5,6,9-三辛基二吲哚并吡咯、0.164克(0.197mmol)3,8-二嚬呐醇硼酸酯-5,6,9-三辛基-9-甲苯基二吲哚并吡咯、0.8毫升四乙基氢氧化铵(20％)、0.6毫升二氧六环、3毫升甲苯于聚合管中，换氩气三次，90摄氏度反应48小时。加入30毫克对甲基苯硼酸和1毫升二氧六环反应24小时，加入0.5毫升对溴甲苯和0.5毫升甲苯反应24小时。冷却，加入稀盐酸搅拌，甲苯萃取，浓缩，用甲醇沉淀，得到粗产物。经过多次溶解、沉淀提纯，最后得到91毫克聚5,6,9-三辛基二吲哚并吡咯3,8-基，产率40％。1H NMR(400 MHz,o-dichlorobenzene,ppm):8.349(s,2H),8.130(m,4H),4.839(m,4H),4.567(m,4H),2.249(m,2H),2.017(m,4H),1.605(s,24H),1.55～1.25(m,30H),1.104(t,6H),1.014(t,3H).
实施例2
(1)3,8-二溴-5,6-二氢-9-甲苯基二吲哚并吡咯的合成
合成路线如下：
100毫升单口瓶中加入0.126克(0.23mmol)二(2-硝基-4-溴苯)甲苯基吡咯，10毫升亚磷酸三乙酯，换氩气三次，160摄氏度反应5小时。反应结束后减压蒸馏除去过量的亚磷酸三乙酯，用硅胶过柱，得到62毫克3,8-二溴-5,6-二氢-9-甲苯基二吲哚并吡咯，产率55％。1H NMR(400 MHz,DMSO,ppm):11.148(s,2H),7.653(m,4H),7.487～7.377(m,4H),7.111(d,J＝8.4,2H).
(2)3,8-二溴-5,6-二正辛基-9-甲苯基二吲哚并吡咯的合成
合成路线如下：
取0.123克(0.25mmol)3,8-二溴-5,6-二氢-9-甲苯基二吲哚并吡咯，84毫克(0.75mmol)特丁醇钾，换氩气三次，注入THF 10毫升，80℃加热搅拌回流至澄清，冷却，注入0.193克(1mmol)C8H17Br，回流过夜。冷却加水，加乙酸乙酯萃取，硫酸镁干燥。过滤，旋除溶剂，得到粗产物。用硅胶过柱，得到0.169克3,8-二溴-5,6-二正辛基-9-甲苯基二吲哚并吡咯，产率94％。1H NMR(400 MHz,o-dichlorobenzene,ppm):7.957(d,J＝8.0,2H),7.828～7.796(m,4H),7.570(d,J＝8.0,2H),7.428(d,J＝8.8,2H),4.548(m,4H),2.607(s,3H),2.100(m,4H),1.601(m,4H),1.50～1.30(m,16H),1.121(t,6H).
(3)3,8-二嚬呐醇硼酸酯-5,6-二正辛基-9-甲苯基二吲哚并吡咯的合成
合成路线如下：
取0.287克(0.4mmol)3,8-二溴-5,6-二正辛基-9-甲苯基二吲哚并吡咯，0.304克(1.2mmol)联二嚬呐醇硼酸酯，0.235克(2.4mmol)醋酸钾，24毫克1,1'-二(二苯膦基)二茂铁二氯化钯(II)(PdCl2(dppf))，换氩气三次，注入无水二氧六环10毫升，80摄氏度反应24小时。冷却，旋除二氧六环，加水和二氯甲烷分层，有机层加硫酸镁干燥。过滤，旋除溶剂，将粗产物过柱得到220毫克3,8-二嚬呐醇硼酸酯-5,6-二正辛基-9-甲苯基二吲哚并吡咯，产率68％。1H NMR(400 MHz,o-dichlorobenzene,ppm):8.376(s,2H),8.081～8.005(m,6H),7.529(d,J＝8,2H),4.625(m,4H),2.563(s,3H),2.071(m,4H),1.503(s,24H),1.484(m,8H),1.373(m,12H),1.121(t,6H).
(4)聚5,6-二正辛基-9-甲苯基二吲哚并吡咯3,8-基的合成
合成路线如下：
取0.28毫克醋酸钯(PdOAc2)、1.83毫克三(邻甲苯基)膦(P(o-Toly)3)、0.141 克(0.197mmol)3,8-二溴-5,6-二正辛基-9-甲苯基二吲哚并吡咯、0.160克(0.197mmol)3,8-二嚬呐醇硼酸酯-5,6-二正辛基-9-甲苯基二吲哚并吡咯、0.8毫升四乙基氢氧化铵(20％)、0.6毫升二氧六环、3毫升甲苯于聚合管中，换氩气三次，90摄氏度反应48小时。加入30毫克对甲基苯硼酸和1毫升二氧六环反应24小时，加入0.5毫升对溴甲苯和0.5毫升甲苯反应24小时。冷却，加入稀盐酸搅拌，甲苯萃取，浓缩，用甲醇沉淀，得到粗产物。经过多次溶解、沉淀提纯，最后得到106毫克聚5,6-二正辛基-9-甲苯基二吲哚并吡咯3,8-基，产率48％。
Claims (10)
1.聚3,8-二吲哚并吡咯，其特征在于，具有如下结构：
其中，R1是C6～C20的烷基链；R2为C6～C20的烷基链或芳香基团，n为≥1的整数。
2.根据权利要求1所述的聚3,8-二吲哚并吡咯，其特征在于，所述R1为下列结构中的一种：
C6H13、C8H17、C10H21、C12H25、C16H33、C20H41。
3.根据权利要求2所述的聚3,8-二吲哚并吡咯，其特征在于，所述R1为下列结构中的一种：
4.根据权利要求1或2或3所述的聚3,8-二吲哚并吡咯，其特征在于，所述芳香基团为：
其中，R为C0～C20的烷基或者烷氧基。
5.根据权利要求4所述的聚3,8-二吲哚并吡咯，其特征在于，所述R为CH3、C2H7、C4H9、C6H13O、C8H17O、C10H21O、C12H25O、C16H33O或C20H41O。
6.根据权利要求5所述的聚3,8-二吲哚并吡咯，其特征在于，所述R为下列结构中的一种：
7.根据权利要求1或2或3所述的聚3,8-二吲哚并吡咯，其特征在于，当R2为烷基链时，结构选自上述R1中的一种。
8.根据权利要求1～7任意一项所述聚3,8-二吲哚并吡咯的制备方法，其特征在于，将二(2-硝基-4-溴苯)吡咯衍生物和亚磷酸三乙酯或者三苯基膦反应，得到3,8-二溴吲哚并吡咯衍生物；在3,8-二溴吲哚并吡咯衍生物上接上烷基后，通过Miyaura反应再将3,8-二溴吲哚并吡咯转化为相应的硼酸酯，将3,8-二溴吲哚并吡咯和它的硼酸酯进行聚合反应，得到聚3,8-二溴吲哚并吡咯。
9.根据权利要求8所述的制备方法，其特征在于，所述3,8-二溴吲哚并吡咯衍生物通过Suzuki或者Yamamoto方法聚合。
10.权利要求1～7任意一项所述聚3,8-二溴吲哚并吡咯的应用，其特征在于，所述聚3,8-二溴吲哚并吡咯应用于电致发光、光伏电池、非线性光学、薄膜场效应晶体管、记忆材料和传感领域。
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