使用腙引发剂的无金属开环易位聚合反应。
Metal-Free Ring-Opening Metathesis Polymerization with Hydrazonium Initiators.
作者信息
Quach Phong K, Hsu Jesse H, Keresztes Ivan, Fors Brett P, Lambert Tristan H
机构信息
Department of Chemistry and Chemical Biology, Cornell University, 122 Baker Laboratory, Ithaca, NY 14853, USA.
出版信息
Angew Chem Int Ed Engl. 2022 Jun 13;61(24):e202203344. doi: 10.1002/anie.202203344. Epub 2022 Apr 13.
Abstract
The ring-opening metathesis polymerization (ROMP) of cyclopropenes using hydrazonium initiators is described. The initiators, which are formed by the condensation of 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers by a sequence of [3+2] cycloaddition and cycloreversion reactions. This process generates short chain polyolefins (M ≤9.4 kg mol ) with relatively low dispersities (Đ≤1.4). The optimized conditions showed efficiency comparable to that achieved with Grubbs' 2 generation catalyst for the polymerization of 3-methyl-3-phenylcyclopropene. A positive correlation between monomer to initiator ratio and degree of polymerization was revealed through NMR spectroscopy.
摘要
描述了使用腙引发剂进行环丙烯的开环易位聚合（ROMP）。这些引发剂由2,3-二氮杂双环[2.2.2]辛烷与醛缩合形成，通过一系列[3+2]环加成和环化反转反应使环丙烯单体聚合。该过程生成具有相对较低分散度（Đ≤1.4）的短链聚烯烃（M≤9.4 kg·mol⁻¹）。优化条件下的效率与使用格拉布催化剂第二代催化3-甲基-3-苯基环丙烯聚合所达到的效率相当。通过核磁共振光谱揭示了单体与引发剂比例和聚合度之间的正相关关系。
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