Shi Yang, Bai Tianwen, Bai Wei, Wang Zhe, Chen Ming, Yao Bicheng, Sun Jing Zhi, Qin Anjun, Ling Jun, Tang Ben Zhong
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, P.R. China.
Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, P.R. China.
Chemistry. 2017 Aug 10;23(45):10725-10731. doi: 10.1002/chem.201702966. Epub 2017 Jul 27.
Alkyne-based click polymerizations have been well-established. However, in order to expand the family to synthesize polymers with new structures and novel properties, new types of click polymerizations are highly demanded. In this study, for the first time, we established a new efficient and powerful phenol-yne click polymerization. The activated diynes and diphenols could be facilely polymerized in the presence of the Lewis base catalyst of 4-dimethylaminopyridine (DMAP) under mild reaction conditions. Regio- and stereoregular poly(vinylene ether ketone)s (PVEKs) with high molecular weights (up to 35 200) were obtained in excellent yields (up to 99.0 %). The reaction mechanism was well explained under the assistance of density functional theory (DFT) calculation. Furthermore, since the vinyl ether sequence acts as a stable but acid-liable linkage, the polymers could be decomposed under acid conditions, rendering them applicable in biomedical and environmental fields.
基于炔烃的点击聚合反应已经得到了充分的发展。然而，为了扩展该家族以合成具有新结构和新性能的聚合物，新型的点击聚合反应是非常必要的。在本研究中，我们首次建立了一种新型高效且强大的苯酚-炔点击聚合反应。在4-二甲基氨基吡啶（DMAP）的路易斯碱催化剂存在下，活化的二炔和二酚可以在温和的反应条件下轻松聚合。以优异的产率（高达99.0%）获得了具有高分子量（高达35200）的区域和立体规整的聚（亚乙烯基醚酮）（PVEK）。在密度泛函理论（DFT）计算的辅助下，反应机理得到了很好的解释。此外，由于乙烯基醚序列作为一种稳定但对酸敏感的连接键，聚合物可以在酸性条件下分解，使其适用于生物医学和环境领域。
