A Mechanoredox Catalyst Facilitates ATRP of Vinylcyclopropanes
Jialin Wang, Longfei Zhang, Du Chen, Chenyu Wang, Ziye Ren, Zhao Wang（王召）*
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key,Laboratory of Advanced Functional Polymer Design and Application, Suzhou Key Laboratory of Macromolecula Design and Precision Synthesis, College of Chemistry, Chemical Engineering, and Materials Science, Soochow University, Suzhou 215123, China
Macromolecules, 2024, 57, 6267−6274
Abstract: Radical ring-opening polymerization (rROP) of vinylcyclopropanes (VCPs) represents an important class of polymerization reactions. Despite the versatility of atom transfer radical polymerization (ATRP) in accessing well-defined polymers, the rROP of VCPs by Cu-catalyzed ATRP remains a formidable challenge. In this study, we propose an efficient mechanically controlled ATRP (mechano-ATRP) approach for different VCPs. This process utilized a mesoporous ZnO (m-ZnO), which effectively prevents Cu catalyst poisoning and promotes the rROP process. The coordination environment of VCP with Cu and a polymer on the m-ZnO surface was confirmed by experimental observations and calculations. The mechano-ATRP yielded poly(VCPs) with a predictable molecular weight, low dispersity, and high chain-end fidelity. This method was employed in the vinylcyclopropane-based resin curing process. The incorporation of m-ZnO can enhance the mechanical properties and reduce the volume shrinkage of the resin. Furthermore, the application of the m-ZnO film as an external catalyst enabled the production of a transparent resin.
链接：//pubs.acs.org/doi/10.1021/acs.macromol.4c00981
