Design and Optimization of Non-Fluorous CO2-Philic Polymers: FTIR and Phase Behavior Investigations

非氟亲 CO2 聚合物的设计和优化：FTIR 和相行为研究

• 批准号: 0207781
• 负责人: Christopher Roberts
• 金额: $ 16.22万
• 依托单位: Auburn University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-01 至 2006-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0207781&HistoricalAwards=false
• 关键词: Design; Optimization; Non; Fluorous; CO2

The application of CO2 to chemical processing continues to elicit significant interest, as CO2 generally poses fewer hazards than conventional organic solvents. At one time it was thought that CO2 could simply replace many organic solvents, but subsequent work showed that CO2 is a rather feeble solvent, and hence unrealistically high pressures are needed to dissolve compounds of interest. The discovery during the 1990's of "CO2-philes" suddenly rendered a number of applications technically possible, greatly raising interest in CO2 as a solvent. These new CO2-philes, primarily fluoropolymers, allowed a host of new applications for CO2, from heterogeneous polymerization to homogeneous catalysis. Although fluorinated amphiphiles were technically successful, their high cost renders the economics of a process unfavorable unless the ihCO2-philelo can be recycled at greater than 99% efficiency. Complicating matters further, recycle of additives from a high-pressure process is neither easy nor inexpensive. The drawbacks inherent to the useof fluorinated precursors have greatly inhibited the commercialization of most new applications for CO2, and thus the full promise of CO2-based technology has yet to be realized. The PI has investigated the design of non-fluorous CO2-philes. To date, he has used a set of simple heuristics to design three types of non-fluorous CO2- phile; he expects that others will ultimately be found, greatly broadening the applicability of CO2 as a solvent.The number of possible design variables (copolymer composition and topology) creates an impractically large program if we continue to synthesize and test all potentially useful structures. Further, conventional thermodynamic models are incapable of predicting the behavior of all of the possible permutations. Consequently, The PI will conduct a coordinated program between the University of Pittsburgh and Auburn University whose ultimate aim is to fully understand the effect of composition and topology on the phase behavior of our new CO2-philes in carbon dioxide. He will to combine targeted synthesis, measurement of selected thermophysical properties, high pressure FT-IR, and development of an accurate potential function from first principles to mathematically describe the thermodynamics of mixing of his materials with CO2. Success will allow himto numerically optimize the structure of non-fluorous CO2-philes.The program described herein involves a fully integrated project at both the University of Pittsburgh (E.J. Beckman, R.M. Enick, J.K. Johnson) and Auburn University (C.B. Roberts). The tasks to be performed at Auburn University (C.B. Roberts) include both phase behavior and FTIR studies, where high pressure IR measurements will be employed to evaluate the strength of specific interactions of CO2 with the Lewis base groups incorporated into our model polymers. The high pressure IR work provides both input to the synthetic design and the construction of an accurate potential model for CO2-polymer interactions.

二氧化碳在化学加工中的应用继续引起重大的兴趣，因为二氧化碳通常比传统的有机溶剂造成的危害少。有一次，人们认为二氧化碳可以简单地取代许多有机溶剂，但是随后的工作表明，二氧化碳是一种相当微弱的溶剂，因此需要不切实际的高压来溶解感兴趣的化合物。在1990年代，“二氧化碳手段”的发现突然在技术上突然提出了许多应用程序，这极大地引起了人们对二氧化碳的兴趣。这些新的二氧化碳手段，主要是氟聚合物，允许许多新的二氧化碳应用，从异质聚合到均匀催化。尽管氟化的两亲物在技术上取得了成功，但它们的高成本使工艺的经济学不利，除非可以以超过99％的效率回收IHCO2-PhileLo。更复杂的是，高压过程中添加剂的回收既不容易也不便宜。使用氟化前体固有的缺点极大地抑制了大多数新应用CO2的商业化，因此尚未实现基于CO2的技术的全部希望。 PI研究了非氟二氧化碳的设计。迄今为止，他已经使用了一组简单的启发式方法来设计三种类型的非浮力二氧化碳。他期望最终发现其他人，从而大大拓宽了二氧化碳作为溶剂的适用性。如果我们继续合成并测试所有潜在有用的结构，那么可能的设计变量（共聚物组成和拓扑）的数量就会产生一个不切实际的程序。此外，常规的热力学模型无法预测所有可能排列的行为。因此，PI将在匹兹堡大学和奥本大学之间进行协调的计划，其最终目的是充分了解组成和拓扑对我们在二氧化碳中新二氧化碳的阶段行为的影响。他将结合靶向合成，测量所选的热物理特性，高压FT-IR以及从第一原理的准确潜在功能的发展，从数学上描述其材料与CO2混合的热力学。成功将使他从数字上优化非氟二氧化碳的结构。此处所述的计划涉及匹兹堡大学（E.J. Beckman，R.M. Enick，J.K。Johnson）和奥本大学（C.B. Roberts）的完全集成项目。在奥本大学（C.B. Roberts）执行的任务既包括阶段行为和FTIR研究，又将采用高压红外测量值来评估CO2与列华人基础组的特定相互作用的强度，并纳入了我们的模型聚合物。高压红外工作既提供了合成设计的输入，又为CO2聚合物相互作用的准确潜在模型的构建提供了输入。