文献类型：期刊文献

英文题名：A Novel Approach toward Polyfulvene: Cationic Polymerization of Enediynes

作者：Chen, Shudan[1];Li, Qiaoping[1];Sun, Shiyuan[1];Ding, Yun[1];Hu, Aiguo[1]

机构：[1]East China Univ Sci & Technol, Shanghai Key Lab Adv Polymer Mat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China

年份：2017

卷号：50

期号：2

起止页码：534

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20171703594256);WOS:【SCI-EXPANDED(收录号:WOS:000392887200005)】；

基金：This work was supported by the National Natural Science Foundation of China (21474027, 91023008), Shanghai Shuguang Project (07SG33), New Century Excellent Talents in University, PhD Programs Foundation of Ministry of Education of China, Shanghai Leading Academic Discipline Project (B502), and the "Eastern Scholar Professorship" support from Shanghai Local Government.

语种：英文

外文关键词：Conjugated polymers - Cyclization - Molecular weight distribution - Regioselectivity - Cationic polymerization

摘要：Enediyne compounds have found limited applications in polymer science and material chemistry due to the poor regioselectivity and/or the step-growth nature in their radical polymerizations. However, the cationic cydization of enediynes exhibits a high regioselective 5-exo-dig mechanism, providing a new strategy for the synthesis of polyfulvene derivatives. The expected polymers were successfully produced by cationic polymerization of enediynes induced by CF3SO3H, and a well-defined conjugated structure was confirmed by NMR, IR, and UV-vis spectroscopy. GPC analysis shows a relatively narrow molecular weight distribution, and the molecular weight reaches up to 62.9 kDa. On the other hand, the structural features of the obtained polymers and the mechanism of the cationic polymerization were investigated through kinetic study and MALDI-TOP MS analysis, which revealed a second-order consumption of enediyne monomer and the polymerization being probably terminated through intramolecular abstraction of proton from the neighboring group.