Intramolecular Cyclization Dominating Homopolymerization of Multivinyl Monomers toward Single-Chain Cyclized/Knotted Polymeric Nanoparticles

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• 作者：Yongsheng Gao ; Dezhong Zhou ; Tianyu Zhao ; Xuan Wei ; Sean McMahon ; Jonathan O鈥橩eeffe Ahern ; Wei Wang ; Udo Greiser ; Brian J. Rodriguez ; Wenxin Wang
• 刊名：Macromolecules
• 出版年：2015
• 出版时间：October 13, 2015
• 年：2015
• 卷：48
• 期：19
• 页码：6882-6889
• 全文大小：473K
• ISSN：1520-5835

文摘

Polymerization of multifunctional monomers could produce polymers with different functionalities and novel macromolecular architectures. However, the ability to control the homopolymerization of multivinyl monomers (MVMs) has always been a challenge. Here we demonstrate that the homopolymerization of acrylate based MVMs can be kinetically controlled via Cu⁰-mediated controlled/living radical polymerization in the presence of additional Cu^II, which enables the efficient promotion of intramolecular cyclization and suppression of intermolecular cross-linking. The gelation is effectively delayed over ca. 40% monomer conversion in the concentrated polymerization system ([M] = 40.9 wt %), which is far higher than the Flory鈥揝tockmayer theory predicts. Moreover, closer inspection of the synthesized polymers reveals that single-chain cyclized/knotted polymeric nanoparticles (SCKNPs) are formed due to the nature of one-pot in situ intramolecular reaction and self-cyclization of the propagating polymer chains. This facile method opens a new avenue to the design and synthesis of a broad range of novel single-chain cyclized/knotted polymeric materials.