Tang Jian, Xie Tinghao, Geng Jieting, Hua Jing, Wang Zhaobo
Key Laboratory of Rubber-Plastics, Ministry of Education, Shandong Education, Shandong Provincial Key Laboratory of Rubber-plastics, Qingdao University of Science and Technology, Qingdao, China.
Front Chem. 2021 Apr 1;9:665877. doi: 10.3389/fchem.2021.665877. eCollection 2021.
π-Conjugated polymers are usually prepared by polymerization only. In this perspective article, typical synthesis methods of conjugated polymers are briefly summarized, and a novel strategy for preparing conjugated polymers by rearrangement is proposed. During the metalation process, many conjugated structures were generated in polybutadiene by double bond migration. The effects of reaction time, temperature, and catalyst dosage on the product structure were investigated. Moreover, the structure of the products was confirmed by FTIR, H NMR, and 2D HSQC NMR spectra. Thus, a possible reaction mechanism was proposed, in which polybutadiene generates allylic carbanions in the presence of n-butyllithium, and then the double bonds migrate through the carbanions rearrangement to generate many conjugated structures in the backbone chain. The method shows promise in facile and low-cost synthesis of conjugated polymers without the need for precious metal catalysts.
π共轭聚合物通常仅通过聚合反应制备。在这篇观点文章中，简要总结了共轭聚合物的典型合成方法，并提出了一种通过重排制备共轭聚合物的新策略。在金属化过程中，聚丁二烯通过双键迁移产生了许多共轭结构。研究了反应时间、温度和催化剂用量对产物结构的影响。此外，通过傅里叶变换红外光谱（FTIR）、核磁共振氢谱（¹H NMR）和二维异核单量子相干核磁共振谱（²D HSQC NMR）对产物结构进行了确认。因此，提出了一种可能的反应机理，即聚丁二烯在正丁基锂存在下生成烯丙基碳负离子，然后双键通过碳负离子重排迁移，在主链中生成许多共轭结构。该方法在无需贵金属催化剂的情况下，有望实现共轭聚合物的简便、低成本合成。
