Glass Transition Behavior of the Quaternary Ammonium-Type Ionic Liquid: N, N -Diethyl-N-methyl-N-(2-methoxyethyl)ammonium Bromide-H2O Mixtures

Yukihiro Yoshimura,1 Naohiro Hatano,1 Yusuke Imai,2 Hiroshi Abe,2 Osamu Shimada,3 and Tomonori Hanasaki3

1Department of Applied Chemistry, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan
2Department of Materials Science and Engineering, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan
3Department of Applied Chemistry, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan

Journal of Thermodynamics
Volume 2012, Article ID 575728, 6 pages

Abstract
By a simple differential thermal analysis (DTA) system, the concentration dependence of the glass transition temperatures (Tg s) for the quaternary ammonium-type ionic liquid, N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bromide [DEME][Br] and H2O mixtures, after quick precooling was measured as a function of water concentration x (mol% H2O). We compared the results with the previous results of [DEME][I]-H2O and [DEME][BF4]-H2O mixtures in which a double-glass transition behavior was observed. Remarkably, the [DEME][Br]-H2O mixtures basically show one-Tg behavior and the Tg decreases monotonically with increasing H2O content up to around x = 91.5. But it suddenly jumps to higher Tg value at a specific x = 92. At this very limited point, two Tgs (Tg1, Tg2) which we might consider as a transition state from the structure belonging to the Tg1 group to another one due to the Tg2 group were observed. These results clearly reflect the difference in the anionic effects among Br-, I-, and BF4-. The end of the glass-formation region of [DEME][Br]-H2O mixtures is around x = 98.9 and moves to more water-rich region as compared to those of [DEME][BF4]-H2O (x = 96.0) and [DEME][I]-H2O (x = 95.0) mixtures.

Fig. 1
Schematic chemical structure of (a) [DEME]+ cation and (b) bromide anion.


Fig. 2
Schematic DTA warm-up traces of 65.0, 92.0, and 95.0mol% H2O mixed solutions are shown.
Fig. 3.
The requenching procedure for detecting the Tg2 at x = 92.0 is shown.
Fig. 4.
Tg variations as a function of x are shown. For comparison, Tg data of [DEME][I]-H2O and [DEME][BF4]-H2O mixed solutions are also shown. : Tg1, : Tg2, : Tg . (only one glass transition was observed except for the region x = 91.5-92.5).
Fig. 5.
Comparison of the Raman spectra among [DEME][BF4]-H2O, [DEME][I]-H2O, and [DEME][Br]-H2O at x =65 in the liquiud state. Peak intensities are normalized by the strongest peak of CH stretching vibrational mode of [DEME]+ cation. (a) The CH and OH stretching vibrational modes of the solutions and (b) the OH stretching vibrational region.
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Last Modified: Nov. 1, 2011