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  1. Cyclohexene oxide (CHO) is a useful building block for the synthesis of novel materials and is a model substrate for polymerization catalyst development. The driving force for CHO polymerization is derived from its bicyclic structure, which combines the release of the enthalpy from epoxide ring-opening (ca. −15 kcal/mol) and a twist-chair-to-chair conformation shift in the cyclohexane ring (ca. −5 kcal/mol) upon enchainment. The lack of regio-defined functional handles attached to the CHO monomer limits the ability to both pre- and post-functionalize the resultant materials and establish structure–property relationships, which reduces the versatility of currently accessible materials. We report the synthesis of two series of CHO derivatives with butyl, allyl, and halogen substituents in the α and β positions relative to the epoxide ring. Adding substituents to the CHO ring was found to affect polymerization kinetics, with 4-substituted (β) CHO being more reactive than 3-substituted (α) CHO analogs when initiated with a mono(μ-alkoxo)bis(alkylaluminum) pre-catalyst. Polymer thermal properties depended on substituent location and identity. Halogenated CHO rings were most reactive and produced the highest glass transition temperatures in the resultant polymers (up to 105 °C). Density functional theory revealed a possible mechanistic explanation consistent with the observed differences in polymerization rate for the 3- and 4-substituted CHOs derived from a combination of steric and thermodynamic considerations. 
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    Free, publicly-accessible full text available July 11, 2024
  2. null (Ed.)
    We report a partial elucidation of the relationship between polymer polarity and ionic conductivity in polymer electrolyte mixtures comprising a homologous series of nine poly(vinyl ether)s (PVEs) and lithium bis(trifluoromethylsulfonyl)imide. Recent simulation studies have suggested that low dielectric polymer hosts with glass transition temperatures far below ambient conditions are expected to have ionic conductivity limited by salt solubility and dissociation. In contrast, high dielectric hosts are expected to have the potential for high ion solubility but slow segmental dynamics due to strong polymer–polymer and polymer–ion interactions. We report results for PVEs in the low polarity regime with dielectric constants of about 1.3 to 9.0. Ionic conductivity measured for the PVE and salt mixtures ranged from about 10–10 to 10–3 S/cm. In agreement with the predictions from computer simulations, the ionic conductivity increased with dielectric constant and plateaued as the dielectric approached 9.0, comparable to the dielectric constant of the widely used poly(ethylene oxide). 
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