两种含联吡啶配体单体的合成及其聚合反应尝试
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摘要
本论文根据聚合物太阳能电池对聚合物光伏材料的要求,综合共轭聚合物和染料敏化剂的优点,拟将金属染料以侧链的形式通过柔性链挂接到共轭聚合物主链上,这样的聚合物主链既可以保持较高的空穴迁移率,侧链染料的引入又可以大大拓宽聚合物对太阳光谱的吸收范围和增强对太阳光的吸收强度,从而制备出性能优异的光伏材料。
含二联吡啶的噻吩基聚合物的设计与合成。首先合成了一个将联吡啶通过柔性链段连接到噻吩环上的二溴单体M1和2,5-二溴-3-辛基噻吩(化合物6)。其中M1未见文献报道。尝试了GRIM方法聚合,化合物6聚合成功,而M1与化合物6共聚却没有得到相应的共聚产物。没有得到预期聚合物的原因可能是联吡啶单元的引入导致了格氏试剂的失活。后对实验方案进行了调整,拟把二溴单体转化为二醛单体化合物8,但也没有得到目标产物,其原因可能是M1的二联吡啶单元破坏了丁基锂的化学结构。
含二联吡啶的咔唑基聚合物的设计与合成。先将联吡啶单元和咔唑单元用柔性链段连接起来制备中间体化合物11,然后通过Vilsmeier醛基化反应使咔唑基团上生成两个醛基来合成单体M2,再用单体M2与1,4-亚苯基二乙腈通过Knoevenagel反应聚合来制备含二联吡啶的咔唑基聚合物。化合物11已经制备成功。但是再用化合物11制备M2时没有得到目标产物,其原因也可能是由于联吡啶单元的存在对Vilsmeier醛基化反应产生了不利的影响。
According to the requirements of polymeric solar cells, aiming to combine the advantages of dye sensitizer and conjugated polymers, the metal complexes will be attached to conjugated main chain as side-chain pendants through a soft linkage. The conjugated main chain of the polymers can make them have high hole-tansporting ability. And the metal complexes can improve the absorption range and absorption intensity of conjugated polymers. Thus, these polymers should have excellent performance for photovoltaic appliction.
Design and synthesis of conjugated polymers based on thiophene containing bipyridine unit. Dibromo thiophene connected with bipyridine through flexible chain monomer M1 and 2,5-dibromo-3-octyl-thiophene (compound 6) were successfully synthesized. M1 was not reported in the literature. Although compound 6 could be polymerized by GRIM method conveniently, the copolymerization of M1 and compound 6 using the same method was not successful. The reason may be that the bipyridine unit of M1 could damage Grignard Reagent. We also tried to convert the dibromo monomer M1 to dialdehyde monomer compound 8 in an adjusted route, but the target product was not obtained.
Design and synthesis of conjugated polymers based on carbazole containing bipyridine unit. First, compound 11 will be synthesized by connecting carbazole unit with bipyridine unit through soft linkage. Then, M2 will be synthesized by attaching two aldehyde groups to the carbazole unit of compound 11 through Vilsmeier reaction. Finally, M2 and 1,4-phenylenediacetonitrile will be copolymerized through Knoevenagel reaction. The intermediate compound 11 was successfully synthesized. Whereas, the translation of compound 11 to M2 was not successful, The reason may be that the bipyridine unit adversely affected the Vilsmeier reaction.
含二联吡啶的噻吩基聚合物的设计与合成。首先合成了一个将联吡啶通过柔性链段连接到噻吩环上的二溴单体M1和2,5-二溴-3-辛基噻吩(化合物6)。其中M1未见文献报道。尝试了GRIM方法聚合,化合物6聚合成功,而M1与化合物6共聚却没有得到相应的共聚产物。没有得到预期聚合物的原因可能是联吡啶单元的引入导致了格氏试剂的失活。后对实验方案进行了调整,拟把二溴单体转化为二醛单体化合物8,但也没有得到目标产物,其原因可能是M1的二联吡啶单元破坏了丁基锂的化学结构。
含二联吡啶的咔唑基聚合物的设计与合成。先将联吡啶单元和咔唑单元用柔性链段连接起来制备中间体化合物11,然后通过Vilsmeier醛基化反应使咔唑基团上生成两个醛基来合成单体M2,再用单体M2与1,4-亚苯基二乙腈通过Knoevenagel反应聚合来制备含二联吡啶的咔唑基聚合物。化合物11已经制备成功。但是再用化合物11制备M2时没有得到目标产物,其原因也可能是由于联吡啶单元的存在对Vilsmeier醛基化反应产生了不利的影响。
According to the requirements of polymeric solar cells, aiming to combine the advantages of dye sensitizer and conjugated polymers, the metal complexes will be attached to conjugated main chain as side-chain pendants through a soft linkage. The conjugated main chain of the polymers can make them have high hole-tansporting ability. And the metal complexes can improve the absorption range and absorption intensity of conjugated polymers. Thus, these polymers should have excellent performance for photovoltaic appliction.
Design and synthesis of conjugated polymers based on thiophene containing bipyridine unit. Dibromo thiophene connected with bipyridine through flexible chain monomer M1 and 2,5-dibromo-3-octyl-thiophene (compound 6) were successfully synthesized. M1 was not reported in the literature. Although compound 6 could be polymerized by GRIM method conveniently, the copolymerization of M1 and compound 6 using the same method was not successful. The reason may be that the bipyridine unit of M1 could damage Grignard Reagent. We also tried to convert the dibromo monomer M1 to dialdehyde monomer compound 8 in an adjusted route, but the target product was not obtained.
Design and synthesis of conjugated polymers based on carbazole containing bipyridine unit. First, compound 11 will be synthesized by connecting carbazole unit with bipyridine unit through soft linkage. Then, M2 will be synthesized by attaching two aldehyde groups to the carbazole unit of compound 11 through Vilsmeier reaction. Finally, M2 and 1,4-phenylenediacetonitrile will be copolymerized through Knoevenagel reaction. The intermediate compound 11 was successfully synthesized. Whereas, the translation of compound 11 to M2 was not successful, The reason may be that the bipyridine unit adversely affected the Vilsmeier reaction.
引文
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