Guo Hao-Xuan, Takahara Hiroshi, Imai Yusuke, Aota Hiroyuki
Department of Chemistry and Materials Engineering, Kansai University, Suita 564-8680, Osaka, Japan.
Polymers (Basel). 2022 Jun 17;14(12):2472. doi: 10.3390/polym14122472.
Bandgap energy is one of the most important properties for developing electronic devices because of its influence on the electrical conductivity of substances. Many methods have been developed to control bandgap, one of which is the realization of conducting polymers using narrow-bandgap polymers; however, the preparation of these polymers is complex. In this study, water-soluble, narrow-bandgap polymers with reactive groups were prepared by the addition-condensation reaction of pyrrole (Pyr), benzaldehyde-2-sulfonic acid sodium salt (BS), and aldehyde-containing reactive groups (aldehyde and pyridine) for post-crosslinking. Two types of reactions, aldehyde with -phenylenediamine and pyridine with 1,2-dibromoethylene, were carried out for the π-conjugated post-crosslinking between polymers. The polymers were characterized by proton nuclear magnetic resonance (H-NMR), thermogravimetric/differential thermal analysis (TG/DTA), UltraViolet-Visible-Near InfraRed spectroscopy (UV-Vis-NIR), and other analyses. The bandgaps of the polymers, calculated from their absorption, were less than 0.5 eV. Post-crosslinking prevents resolubility and develops electron-conducting routes between the polymer chains for π-conjugated systems. Moreover, the post-crosslinked polymers maintain their narrow bandgaps. The electrical conductivities of the as-prepared polymers were two orders of magnitude higher than those before the crosslinking.
带隙能量是开发电子器件最重要的特性之一,因为它会影响物质的电导率。人们已经开发出许多控制带隙的方法,其中之一是使用窄带隙聚合物来制备导电聚合物;然而,这些聚合物的制备过程很复杂。在本研究中,通过吡咯(Pyr)、苯甲醛-2-磺酸钠盐(BS)和含醛反应性基团(醛和吡啶)的加成缩合反应制备了具有反应性基团的水溶性窄带隙聚合物,用于后续交联。进行了两种类型的反应,即醛与对苯二胺的反应以及吡啶与1,2-二溴乙烯的反应,以实现聚合物之间的π共轭后交联。通过质子核磁共振(H-NMR)、热重/差热分析(TG/DTA)、紫外-可见-近红外光谱(UV-Vis-NIR)等分析对聚合物进行了表征。根据聚合物的吸收计算得出的带隙小于0.5 eV。后交联可防止聚合物再溶解,并为π共轭体系在聚合物链之间形成电子传导路径。此外,后交联聚合物保持其窄带隙。所制备聚合物的电导率比交联前高出两个数量级。