GOALI: Design and Evaluation of Room Temperature Ionic Liquids for Green Chemical Processing

离子液体（Ionic Liquids，IL）是一种有机盐，在室温下纯态为液体。典型的IL基于与多种阴离子配对的大体积吡啶钥或咪唑钥阳离子。分子的庞大性和不对称性阻止了促进结晶的容易堆积，因此这些材料表现出低熔点。虽然离子液体是有机溶剂，但它们表现出消失的小蒸气压，因此不存在逃逸到大气中以及暴露于工人的最普遍的途径-蒸发。低蒸气压也使这些溶剂更安全，因为闪点将比传统有机溶剂高得多。研究表明，离子液体是各种工业相关反应的优良溶剂。然而，由于缺乏有关离子液体物理性质和相行为的文献资料，限制了离子液体的应用。基于1-甲基咪唑盐的离子液体结构上的排列数非常大，结构和性质之间的相关性目前还不存在，当前的目标是探索离子液体的化学结构和其物理性质之间的关系，包括其与CO2，其他小分子，水和有机溶质的相行为。该方法是使用分子模拟与实验测量相结合，以开发可用于指导设计的结构/性能关系，所需的性能。特别是，我们建议合成各种咪唑类离子液体，并测量其纯组分的熔点和密度。 建议开发分子力场的Monte Carlo模拟，充分再现纯组分的数据。 建议使用几种不同的高压气/液平衡装置、重量分析技术和色谱法来测量这些离子液体中的一些与有机物、水、CO2和O2或H2的相行为。 为了补充这些实验工作，建议使用吉布斯系综蒙特卡罗模拟离子液体与小分子如CO2或H2的相行为。 基于测量和建模，我们建议开发IL结构与其物理性质和相行为之间的关系。这些信息对于评估离子液体在各种重要工业应用中的作用至关重要（将在未来项目中开发）。 一些实例包括使用Ils作为用于反应和分离的环境友好溶剂，作为用于有效氢化、氧化和加氢化学的介质，使用CO2作为安全吸附制冷系统以取代CFC和HFC，作为氢储存介质，以及作为用于聚合物的凝胶纺丝的溶剂。

ABSTRACTCTS-9987627Brennecke, JoanUniversity of Notre DameIonic liquids (ILs) are organic salts that in their pure state are liquids at ambient temperature. The typical IL is based on a bulky pyridinium or imidazolium cation paired with a variety of anions. The bulkiness and asymmetry of the molecule prevents the easy packing that promotes crystallization, and hence these materials exhibit low melting points. Although ILs are organic solvents, they exhibit vanishing small vapor pressures, and thus the most prevalent route for escape to the atmosphere and also exposure to workers -- evaporation -- is absent. Low vapor pressure also renders these solvents safer, as flash points will be much higher than for traditional organic solvents. Research has shown that ILs are excellent solvents for a variety of industrially relevant reactions. However, the use of ILs is limited by the paucity of literature data on their physical properties and phase behavior. The number of permutations on the structure of even simple ILs based on 1-methyl imidazolium is extremely large and correlations between structure and properties do not currently exist.The immediate goal is to explore the relationship between the chemical structure of an IL and its physical properties, including its phase behavior with CO2, other small molecules, water, and organic solutes. The methodology is to use molecular simulations in concert with experimental measurements to develop structure/property relationships that could be used to guide the design, desired properties. In particular, we propose to synthesis a variety of imidazolium-based ionic liquids and measure their pure component melting points and densities. It is proposed to develop molecular forcefields for Monte Carlo simulations that adequately reproduce the pure component data. It is proposed to measure the phase behavior of some of these ionic liquids with organics, water, CO2 and O2 or H2 using several different high pressure vapor/liquid equilibrium apparatuses, gravimetric techniques, and chromatography. To complement these experimental efforts, it is proposed to use Gibbs ensemble Monte Carlo to simulate the phase behavior of an ionic liquid with small molecules such as CO2 or H2. Base upon the measurements and modeling, we propose to develop relationships between the IL structure and its physical properties and phase behavior. This information will be vital to the evaluation of ILs for a variety of important industrial applications (to be developed in future projects. Some examples include the use of Ils as environmentally benign solvents for reactions and separations, as a medium for efficient hydrogenation, oxidation and hydroformylation chemistry, with CO2 as a safe adsorption refrigeration system to replace CFCs and HFCs, as a hydrogen storage medium, and as a solvent for the gel-spinning of polymers.