Coordinate anionic ring‐opening polymerization of oxetanes with aluminum benzyl alcoholate bis(2,6‐di‐<i>tert</i>‐butyl‐4‐methylphenolate)

Kanoh, Shigeyoshi; Takemura, Atsushi; Fukuda, Koh-ichi; Chinwanitcharoen, Charoen; Motoi, Masatoshi

doi:10.1002/pola.20359

Cited by 7 publications

(3 citation statements)

References 22 publications

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“…12a Even more difficulty was found for the polymerization of 8 (entries 11 and 12 in Table S1). Other initiators reported for the anionic coordinated ring-opening polymerization, such as aluminum complexes, 16 were not effective for the polymerization of 8, which reacted rather with the radical groups to undergo decomposition.…”

Section: Resultsmentioning

confidence: 97%

Synthesis and Charge Transport Properties of Redox-Active Nitroxide Polyethers with Large Site Density

et al. 2010

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To maximize the theoretical redox capacity of polymers containing cyclic nitroxides as redox-active pendant groups for high-density charge storage application, a compact five-membered ring with the smallest equivalent weight among the robust cyclic nitroxides was directly bound to a poly(ethylene oxide) chain. 2,2,5,5-Tetramethyl-3-oxiranyl-3-pyrrolin-1-oxyl was synthesized and polymerized via anionic coordinated ring-opening polymerization utilizing diethyl zinc/H2O as an initiator. The unpaired electron in the monomer survived during the polymerization, giving rise to a high density redox polymer with a weight-specific theoretical capacity of 147 mA h/g. Cyclic voltammetry of the polymer layer confined at the surface of an electrode revealed a large redox capacity comparable to the theoretical capacity, which was ascribed to the efficient swelling and yet insoluble properties of the polyether in electrolyte solutions by virtue of the high molecular weight of >105 and adhesive properties allowing immobilization of the layer on the electrode surface. The redox capacity also indicated that the ionophoric polyether matrix accommodated electrolyte anions through the polymer/electrolyte interface to neutralize positive charges produced by the oxidation of the neutral radicals at the polymer/electrode interface. The diffusion coefficient for the redox gradient-driven charge hopping process corresponded to a large second-order rate constant in the order of 107 M−1 s−1, which suggested an efficient electron self-exchange reaction throughout the polymer layer due to the large redox site population and hence to the small intersite distance. Test cells fabricated with a polymer/carbon fiber composite layer on an aluminum current collector as the cathode and a Li anode sandwiching an electrolyte layer were capable of charging and discharging as a secondary battery with an output voltage near 3.7 V and were durable for more than 103 charging−discharging cycles without substantial degradation.

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Section: Resultsmentioning

confidence: 97%

Synthesis and Charge Transport Properties of Redox-Active Nitroxide Polyethers with Large Site Density

et al. 2010

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“…16 Attempts to polymerize 3 or 4 with the Lewis acidic BF 3 or other cationic initiators were unsuccessful, resulting from the undesired oxidation of the radical pendants. Initiators reported for anionic coordinated ringopening polymerization, such as aluminum complexes, 17 were not effective for the polymerization of 3 and 4 (entry 11), which reacted with the radical groups to undergo decomposition.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Radical-Bearing Polyethers as an Electrode-Active Material for Organic Secondary Batteries

et al. 2008

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“…4 Aluminum phenoxide was synthesized and used differently in several chemical processes. It has been utilized in an isolated or in situ generated forms [27,[29][30][31]. In fact, the synthesis of aluminum phenoxide was first reported over 130 years ago [32].…”

Section: Introductionmentioning

confidence: 99%

Structural and spectroscopic characterizations of aluminum phenoxide

Mohammadnezhad

Amini

Khavasi

et al. 2016

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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A synthetic route to obtain crystalline aluminum phenoxide was established. Its molecular structure in solid-state and solution is unambiguously determined by single-crystal X-ray diffraction and (1)H, (13)C and (27)Al NMR spectroscopy. The single-crystal X-ray analysis revealed the presence of the dimeric THF adduct [Al(OPh)3·THF]2 with a disordered trigonal bipyramidal geometry at the aluminum atom which is bonded to a THF ligand, two terminal and two bridging phenoxy groups (OPh). The solution behavior of the title compound was investigated by (27)Al NMR in non-coordinating (CDCl3) as well as coordinating (THF) solvents at different temperatures. The obtained results indicate the presence of four- and five-coordinate species in solution.

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Coordinate anionic ring‐opening polymerization of oxetanes with aluminum benzyl alcoholate bis(2,6‐di‐tert‐butyl‐4‐methylphenolate)

Cited by 7 publications

References 22 publications

Synthesis and Charge Transport Properties of Redox-Active Nitroxide Polyethers with Large Site Density

Synthesis and Charge Transport Properties of Redox-Active Nitroxide Polyethers with Large Site Density

Synthesis and Characterization of Radical-Bearing Polyethers as an Electrode-Active Material for Organic Secondary Batteries

Structural and spectroscopic characterizations of aluminum phenoxide

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