Densely Arrayed Cage-Shaped Polymer Topologies Synthesized via Cyclopolymerization of Star-Shaped Macromonomers

Yoshinobu Mato, Maho Sudo, Hironori Marubayashi, Brian J. Ree, Kenji Tajima, Takuya Yamamoto, Hiroshi Jinnai, Takuya Isono, Toshifumi Satoh

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)


This work reports a facile and versatile ring-opening metathesis polymerization of three- and four-armed star-shaped poly(ϵ-caprolactone) (PCL) macromonomers bearing a norbornenyl group at each chain end using Grubbs' third-generation catalyst under diluted condition to obtain graft polymers (GPs) comprising densely arrayed three- and four-armed cage-shaped grafted PCLs (GPCLs) with narrow dispersity (1.19-1.35) and a controllable number of cage repeating units up to 40 (molecular weight: ∼320 »000 g mol-1). The GPCLs were characterized using nuclear magnetic resonance spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. The cyclopolymerization proceeded via repetitive rapid intramolecular reactions to form cage-shaped units followed by slow intermolecular propagation. This synthesis was applicable to star-shaped poly(l-lactide), poly(trimethylene carbonate), and poly(ethylene glycol). Investigating the structure-property relationships regarding crystallization behavior, hydrodynamic diameter, and viscosity revealed that cage-shaped topological side chains reduced the chain dimensions and mobility compared to their linear and cyclic counterparts.

Original languageEnglish
Pages (from-to)9079-9090
Number of pages12
Issue number19
Publication statusPublished - 2021 Oct 12


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