Designing Complexes for Homogenous Catalysis and Polymerization

该研究项目结合了合成无机化学、催化和聚合，以解决有关利用大量二氧化碳作为原料分子制备更有价值的化学品（包括聚合物）的问题。这项工作涉及基础研究，但具有与社会相关的重要应用。主要目标是制备新的含金属分子，以可控的方式催化二氧化碳与其他小分子的反应。这些反应的产物可以用作溶剂、其他增值化学品或高性能聚合物的前体。***最终，二氧化碳能否与其他废物分子结合产生有价值的产品？例如，环氧丙烷（PO）可以从丙烯中得到，丙烯是炼油和天然气加工的副产品。CO2可与PO反应生成碳酸丙烯或聚碳酸丙烯。碳酸丙烯酯是一种具有高沸点的极性溶剂，也是锂电池中电解质的组成部分。聚碳酸丙烯酯等聚合物可用于制造可降解薄膜，或用于制造汽车坐垫等聚氨酯材料。其他反应物可以从植物物质中获取，如柑橘果皮（柠檬烯氧化物）或林业废弃物（蒎烯氧化物）。以前的工作集中在可调催化剂系统，可以合理地改变，拨出选择性的环状或聚合碳酸盐岩。有了这些系统，现在的兴趣在于聚合物分子量和微观结构的控制。微观结构涉及聚合物中单体的排列（例如，头对尾或头对头的方向，称为区域化学，以及单体基团向上或向下的相对排列，称为战术性）。微观结构对聚合物的熔点、结晶度等物理性能有重要影响，通过精心的催化剂设计，对其进行关键控制。新一代催化剂的基础上廉价和地球丰富的金属（如铬，钴，铁，铝，镁和锌）将被制备。计算研究将有助于深入了解机理细节，并与使用定制设计的反应容器进行的原位光谱分析以及各种质谱分析技术获得的直接实验证据相结合。这些信息将允许进一步调整实验条件和催化剂设计。***长期目标包括开发新的催化系统和从二氧化碳中提取的有用材料，以及为二氧化碳反应和地球丰富金属化学的基础知识做出贡献。这两个目标对于加拿大制造业开发可持续技术和有效利用资源都非常有价值。

This research program combines synthetic inorganic chemistry, catalysis and polymerization to address problems concerning the use of abundant CO2 as a feedstock molecule for preparing more valuable chemicals, including polymers. The work involves fundamental research but with significant applications relevant to society. The primary goal is the preparation of new metal-containing molecules that catalyze the reaction of CO2 with other small molecules in a controlled fashion. The products of these reactions can be used as solvents, precursors to other value-added chemicals or high performance polymers.***Ultimately, can CO2 be combined with other waste molecules to give valuable products? For example, propylene oxide (PO) can be obtained from propene, which is a byproduct of oil refining and natural gas processing. CO2 can be reacted with PO to give propylene carbonate or poly(propylene carbonate). Propylene carbonate is used as a polar solvent with a high boiling point and as a component of electrolytes in lithium batteries. Polymers such as poly(propylene carbonate) are useful as degradable thin films or as components in polyurethane manufacturing for things like automotive seat cushions. Other reactants can be sourced from plant matter such as citrus fruit peels (limonene oxide) or forestry waste (pinene oxide). Previous work focused on tunable catalyst systems that can be rationally altered to dial in selectivity for cyclic or polymeric carbonates. With these systems in hand, interest now lies in the control of polymer molecular weight and microstructure. Microstructure concerns the arrangement of the monomers within the polymer (e.g head-to-tail or head-to-head orientation, known as regiochemistry, and up or down relative arrangement of the monomer groups, known as tacticity). Microstructure has significant influence on the physical properties of the polymer, like melting point and crystallinity and its crucial control will be obtained through careful catalyst design. New generations of catalysts based on inexpensive and earth abundant metals (e.g. chromium, cobalt, iron, aluminum, magnesium and zinc) will be prepared. Computational studies will assist with insight into mechanistic details, partnered with direct experimental evidence obtained by in-situ spectroscopy performed using a custom designed reaction vessel, as well as by a variety of mass spectrometry techniques. This information will permit the further tuning of experimental conditions and catalyst design. ***Long-term goals include the development of new catalytic systems and useful materials derived from CO2, as well as contributing to the fundamental knowledge of reactions of CO2 and the chemistry of earth abundant metals. Both of these goals are extremely valuable for developing sustainable technologies and efficient use of resources for the manufacturing industry in Canada.