Ring-Opening and Ring-Forming Polymerization of 1,2:5,6:9,10-Triepoxydecane Leading to a Highly Regioselective Polymer Consisting of Octahydrobifuranyl Unit

Kakuchi, Toyoji; Nonokawa, Ryuji; Umeda, Satoshi; Satoh, Toshifumi; Yokota, Kazuaki

doi:10.1021/ma991449j

Cited by 8 publications

(6 citation statements)

References 13 publications

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“…We envisioned that extending this approach would directly yield the corresponding cage-GPs from star-shaped macromonomers containing polymerizable groups at each chain end. A few examples of the cascade cyclopolymerization of specially designed multifunctional monomers (e.g., trivinyl, tetrayne, and triepoxide) have been reported previously (Figure b). However, such multifunctional monomers all have a low-molecular degree of freedom.…”

Section: Introductionmentioning

confidence: 82%

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

et al. 2021

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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 cageshaped topological side chains reduced the chain dimensions and mobility compared to their linear and cyclic counterparts.

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Section: Introductionmentioning

confidence: 82%

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

et al. 2021

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“…The nucleophilic ring-opening of the epoxide at the β-position by the bulky tert -butoxy anion liberates a secondary alkoxide anion, which rapidly undergoes subsequent intramolecular 5- exo - tet cyclization to ring-open the second epoxide at the α-position and forms a propagating primary alkoxide anion . The complexity of polymer main-chain structures generated through iRORCCP was further demonstrated in the anionic cascade polymerization of triepoxide 1,2:5,6:9,10-triepoxydecane ( 10 , Scheme B) . This impressive ionic cascade consists of two consecutive 5- exo - tet cyclizations following epoxide ring opening, resulting in a polymer featuring a bis-tetrahydrofuran motif in a single repeating unit.…”

Section: Ionic and Nucleophilic Cascade Polymerizationmentioning

confidence: 99%

“…102 The complexity of polymer main-chain structures generated through iRORCCP was further demonstrated in the anionic cascade polymerization of triepoxide 1,2:5,6:9,10-triepoxydecane (10, Scheme 15B). 103 This impressive ionic cascade consists of two consecutive 5-exo-tet cyclizations following epoxide ring opening, resulting in a polymer featuring a bis-tetrahydrofuran motif in a single repeating unit. Compared to anionic polymerization, cationic polymerizations of such monomers are usually less efficient and the resulting backbone structures may contain more defects.…”

Section: Ionic and Nucleophilic Cascade Polymerizationmentioning

confidence: 99%

Cascade Reactions in Chain-Growth Polymerization

et al. 2020

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While the design and implementation of cascade reactions in organic chemistry and enzymatic biosynthesis flourished in the past decades, cascade reactions in polymerization remain an emerging concept with exciting opportunities. Cascade polymerization techniques can be used to generate polymers in which unique structures and functionalities are incorporated in the backbone of polymers, making them powerful tools to address the ever-increasing demand for new materials with improved functionality and sustainability. This Perspective highlights existing strategies for chain-growth cascade polymerizations following radical, ionic, nucleophilic, and transition metal catalysis mechanisms, with a focus on the design principle and reaction mechanism. Collectively, recent work illustrates the considerable potential and predicts future developments of chain-growth cascade polymerization, an active research field at the intersection of polymer science and organic chemistry.

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“…5A) was shown to undergo a back-to-back simultaneous RO/RC anionic cascade, without evidence of mono-or di-epoxide pendant groups (which would result from propagation before completion of the cascade sequence). 35 Additionally, a spiroketal monomer (14, Fig. 5B) was shown to undergo a cationic RO/RO cascade, without evidence of any single RO repeat units.…”

Section: Ionic Cascade Polymerizationsmentioning

confidence: 99%

Cascade polymerizations: recent developments in the formation of polymer repeat units by cascade reactions

Peterson

Choi

2020

Chem. Sci.

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Ring-Opening and Ring-Forming Polymerization of 1,2:5,6:9,10-Triepoxydecane Leading to a Highly Regioselective Polymer Consisting of Octahydrobifuranyl Unit

Cited by 8 publications

References 13 publications

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

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

Cascade Reactions in Chain-Growth Polymerization

Cascade polymerizations: recent developments in the formation of polymer repeat units by cascade reactions

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