Mechanistic Studies Employing In Situ Infrared Spectroscopy of Reactions Pertinent to Metal-Catalyzed Carbon Dioxide/Epoxide Coupling Processes

采用原位红外光谱对金属催化二氧化碳/环氧化物偶联过程相关反应进行机理研究

• 批准号: 0234860
• 负责人: Donald Darensbourg
• 金额: $ 52.5万
• 依托单位: Texas A&M Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-02-01 至 2006-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0234860&HistoricalAwards=false
• 关键词: Mechanistic; Studies; Employing; Situ; Infrared

This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Prof. Donald J. Darensbourg of Texas A&M University to address the utilization of carbon dioxide in the development of improved synthetic routes for the production of polycarbonates. The current industrial production of these materials is both hazardous and expensive and involves the interfacial polycondensation of phosgene and diols. This research will examine in detail the mechanistic aspects of metal catalyzed carbon dioxide/epoxide coupling reactions employing in situ spectroscopy methods utilizing Fourier-transform infrared attenuated total reflectance (FTIR/ATR) spectroscopy. Selected processes will be investigated both in carbon dioxide swollen organic solvents and in the absence of added solvents where phase behavior is of importance. Experiments are designed to understand the various factors controlling carbon dioxide /epoxide coupling processes involving alicyclic vs aliphatic epoxides with particular emphasis on copolymer vs cyclic carbonate formation. Selected catalyst systems to be examined include those with adjacent nucleophile/epoxide binding sites and those with trans related binding sites (e.g., (salen)Cr(III)Cl). Other studies will explore the development of structural and reactivity models for the industrially prevalent double metal cyanide catalysts (DMC) used in polyether and polycarbonate synthesis. The very important fields of organometallic chemistry, catalyst design, polymer catalysis and characterization provide valuable training for graduate and undergraduate students entering either the academic or industrial work force. Furthermore, these studies heighten students' sensitivities to the roles chemists play in issues of environmental concern. Outreach programs involve high school students in research projects.This research seeks to find new, more environmentally benign ways of producing polycarbonate plastics utilizing carbon dioxide as a synthetic component.

该奖项由德克萨斯A＆M大学的Donald J. Darensbourg教授提供的无机，生物有机和有机金属化学计划支持研究，以解决二氧化碳的利用，以开发出生产多碳酸盐的合成途径。 这些材料的当前工业生产既危险又昂贵，涉及磷酸和二醇的界面多偏。 这项研究将详细研究使用傅立叶转换红外衰减总反射率（FTIR/ATR）光谱法，采用原位光谱法的金属催化二氧化碳/环氧化物偶联反应的机械方面。 选定的过程将在二氧化碳肿胀的有机溶剂中进行研究，并且在没有相位行为的附加溶剂的情况下。 实验旨在理解控制二氧化碳 /环氧化碳耦合过程的各种因素，涉及甲基二氧化碳与脂肪族环氧化物，特别强调共聚物与环状碳酸盐形成。 要检查的选定催化剂系统包括具有邻近亲核/环氧化物结合位点的催化剂系统以及具有反式相关结合位点的催化剂系统（例如（Salen）Cr（iii）CL）。 其他研究将探讨用于多纤维和聚碳酸酯合成的工业普遍的双金属氰化物催化剂（DMC）的结构和反应性模型的发展。有机金属化学，催化剂设计，聚合物催化和表征的非常重要的领域为研究生和本科生提供了宝贵的培训，进入了学术或工业劳动力。 此外，这些研究增强了学生对化学家在环境问题问题上所扮演的角色的敏感性。 外展计划涉及高中学生参与研究项目。本研究旨在寻找新的，更环保的方式，以生产利用二氧化碳作为合成成分的聚碳酸酯塑料。