1. Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts.
- Author
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Yang, Fan, Zhao, Meng, Smith, Darren, Cebe, Peggy, Lucisano, Sam, Allston, Thomas, and Smith, Thomas W.
- Subjects
CONDUCTING polymers ,GLASS transition temperature ,GLASS transitions ,SALTS ,POLYMER solutions - Abstract
The synthesis of 1-butyl-2,3-dimethyl-4-vinylimidazolium triflate, its polymerization, and ion exchange to yield a trio of 1-butyl-2,3-dimethyl-4-vinylimidazolium polymers is described. Irrespective of the nature of the anion, substitution at the 2-position of the imidazolium moiety substantially increases the distance between the anion and cation. The methyl substituent at the 2-position also served to expose the importance of H-bonding for the attractive potential between imidazolium moiety and anions in polymers without a methyl group at the 2-position. The thermal characteristics of poly(1-butyl-2,3-dimethyl-4-vinylimidazolium) salts and corresponding poly(1-ethyl-3-methyl-4-vinylimidazolium) salts were evaluated. While the mid-point glass transition temperatures, T
g -mid, for 1-ethyl-3-methyl-4-vinylimidazolium polymers with CF3 SO3 − , (CF3 SO2 )2 N− and PF6 − counterions, were 153 °C, 88 °C and 200 °C, respectively, the Tg -mid values for 1-butyl-2,3-dimethyl-4vinylimidazolium polymers with corresponding counter-ions were tightly clustered at 98 °C, 99 °C and 84 °C, respectively. This dramatically reduced influence of the anion type on the glass transition temperature was attributed to the increased distance between the center of the anions and cations in the 1-butyl-2,3-dimethyl-4-vinylimidazolium polymer set, and minimal H-bonding interactions between the respective anions and the 1-butyl-2,3-dimethyl-4-vinylimidazolium moiety. It is believed that this is the first observation of substantial independence of the glass transition of an ionic polymer on the nature of its counterion. [ABSTRACT FROM AUTHOR]- Published
- 2022
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