Wu Yongwei, He Benzhao, Wang Jia, Hu Rongrong, Zhao Zujin, Huang Fei, Qin Anjun, Tang Ben Zhong
State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
Department of Chemistry, The Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.
Macromol Rapid Commun. 2017 Feb;38(4). doi: 10.1002/marc.201600620. Epub 2017 Jan 3.
The transition-metal catalyzed and metal-free click polymerizations have been developed as powerful tools for the construction of functional polymers with linear and hyperbranched structures. The latter provides a thorough solution for the completely removing metallic residues from the products encountered in the former. Compared to the activated alkyne-azide metal-free click polymerization, the activated azide-alkyne one is rarely studied. In this Communication, a perfluorophenyl-activated azide of hexane-1,6-diyl-bis(4-azido-2,3,5,6-tetrafluorobenzoate) is rationally designed and facilely prepared. Through systematical optimization of the reaction conditions, an efficient metal-free perfluorophenylazide-alkyne polycycloaddition is established, and polytriazoles with high molecular weights (up to 166 000) and excellent solubility are obtained in excellent yields (up to 93%) under mild reaction conditions. Interestingly, the regioselectivity of the reaction could be fine-tuned by the solvents and diyne monomers. Therefore, this work provides not only a powerful tool for the preparation of functional polytriazoles, but also an attractive method for fine-tuning their regioregularity.
过渡金属催化的无金属点击聚合反应已发展成为构建具有线性和超支化结构的功能聚合物的有力工具。后者为彻底去除前者产物中残留的金属提供了一个完整的解决方案。与活化炔基-叠氮化物无金属点击聚合反应相比，活化叠氮化物-炔基的反应很少被研究。在本通讯中，合理设计并简便制备了己烷-1,6-二基双(4-叠氮基-2,3,5,6-四氟苯甲酸酯)的全氟苯基活化叠氮化物。通过系统优化反应条件，建立了一种高效的无金属全氟苯基叠氮化物-炔基多环加成反应，在温和的反应条件下以优异的产率(高达93%)获得了高分子量(高达166 000)且溶解性优异的聚三唑。有趣的是，反应的区域选择性可以通过溶剂和二炔单体进行微调。因此，这项工作不仅为制备功能化聚三唑提供了一个有力的工具，也为微调其区域规整性提供了一种有吸引力的方法。
