季铵型离子液体:N,N-二乙基-N-甲基-N-(2-甲氧基乙基)溴化铵- h2o混合物的玻璃化转变行为

Y. Yoshimura, N. Hatano, Y. Imai, H. Abe, Osamu Shimada, T. Hanasaki
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引用次数: 1

摘要

采用简单差热分析(DTA)系统,测定了季铵型离子液体N,N-二乙基-N-甲基-N-(2-甲氧基乙基)溴化铵[DEME][Br]与H2O混合物在快速预冷后玻璃化转变温度(𝑇𝑔s)随水浓度(mol% H2O)的变化规律。我们将结果与先前观察到双玻璃转变行为的[DEME][I]-H2O和[DEME][BF4]-H2O混合物的结果进行了比较。值得注意的是,[DEME][Br]-H2O混合物基本表现为一𝑇𝑔行为,并且𝑇𝑔随着H2O含量的增加而单调减小,直至约为91.5。但是它突然跳到更高的𝑇𝑔值在一个特定的值= ~ 92。在这个非常有限的点上,观察到两个𝑇𝑔s(𝑇𝑔1,𝑇𝑔2),我们可以将其视为从属于𝑇𝑔1组的结构到属于𝑇𝑔2组的另一个结构的过渡状态。这些结果清楚地反映了Br−、I−和BF4−之间阴离子效应的差异。与[DEME][Br]-H2O混合物相比,[DEME][BF4]-H2O混合物的玻璃形成区末端在[DEME][Br]-H2O混合物(≥96.0)和[DEME][I]-H2O混合物(≥95.0)的玻璃形成区向富水区域移动。
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Glass Transition Behavior of the Quaternary Ammonium-Type Ionic Liquid: N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium Bromide-H2O Mixtures
By a simple differential thermal analysis (DTA) system, the concentration dependence of the glass transition temperatures (𝑇𝑔s) 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.
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