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

DameIonic liquid （ILs）是一种有机盐，在室温下是纯液态。典型的IL是基于一个庞大的吡啶或咪唑阳离子与各种阴离子配对。分子的体积和不对称阻碍了易于包装，从而促进结晶，因此这些材料表现出低熔点。虽然有机溶剂是有机溶剂，但它们表现出消失的小蒸汽压，因此不存在逃逸到大气中并暴露于工人的最常见途径——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，il是各种工业相关反应的优良溶剂。然而，由于缺乏关于其物理性质和相行为的文献数据，限制了其使用。即使是基于1-甲基咪唑的简单il，其结构上的排列数量也非常多，而且目前还不存在结构与性能之间的相关性。当前的目标是探索IL的化学结构与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。该方法是将分子模拟与实验测量相结合，以开发可用于指导设计和期望性能的结构/性能关系。特别是，我们建议合成各种咪唑基离子液体，并测量它们的纯组分熔点和密度。提出了开发分子力场的蒙特卡罗模拟，充分再现纯组分数据。建议使用几种不同的高压汽液平衡仪、重量技术和色谱法来测量这些离子液体与有机物、水、CO2和O2或H2的相行为。为了补充这些实验成果，建议使用吉布斯系综蒙特卡罗模拟具有小分子（如CO2或H2）的离子液体的相行为。在测量和建模的基础上，我们建议发展IL结构与其物理性质和相行为之间的关系。这一资料对于评价将在今后项目中发展的各种重要工业应用的化学物质至关重要。一些例子包括使用液化气作为反应和分离的环保溶剂，作为高效氢化、氧化和氢甲酰化化学的介质，将二氧化碳作为替代氟氯化碳和氢氟碳化物的安全吸附制冷系统，作为储氢介质，以及作为聚合物凝胶纺丝的溶剂。

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.