Homogeneous Catalysts for the Production of Monomers for Sustainable Polymers from CO2 and Diols

1)最初的重点是开发用于CO2和二醇偶联以形成6元环状碳酸酯的催化剂。2）开发用于其他小分子偶联的催化方案，例如CS23）开发用于开环聚合反应的催化剂基于Buchard实验室先前发表的结果，最初的研究将旨在开发用于二氧化碳与1，3二醇以形成环状碳酸酯。人们希望这将通过利用受挫的布朗斯台德碱：刘易斯酸对策略来实现。将采用双边实验和计算方法，用DFT计算补充实际数据。这些计算结果将用于实验室的进一步研究，一旦实现，将进行研究以阐明反应环化步骤的机理途径。智能催化剂设计可以允许调节环化步骤的方向，潜在地导致形成先前不可接近的环状碳酸酯单体。此外，我们希望应用于CO2和二醇偶联的催化策略也可以应用于其他环化试剂（例如，硫化碳、硅烷、硫化羰等）。除此之外，还将研究用于聚合反应的新型催化体系（有机催化剂和金属络合物），包括研究可转换的催化剂和用于流动应用的表面固定化。

1) Initial focus on the development of catalysts for CO2 and diol coupling to form 6 membered cyclic carbonates.2) Develop catalytic protocols for other small molecule coupling e.g. CS23) Develop catalysts for ring opening polymerisation reactionsBuilding on previously published results from the Buchard laboratory, the initial research will aim to develop a catalytic protocol for the coupling of carbon dioxide with 1,3 diols to form cyclic carbonates. It is hoped this will be achieved through utilisation of a frustrated Bronsted base: Lewis acid pair strategy. A bilateral experimental and computational approach will be adopted, by supplementing practical data with DFT calculations. Such calculations will be used to inform further study within the laboratory.Once achieved, research will be undertaken to elucidate the mechanistic pathway of the cyclisation step of the reaction. Intelligent catalyst design may allow for tuned direction of the cyclisation step, potentially leading to formation of previously inaccessible cyclic carbonate monomers. In addition, it is hoped the catalytic strategy as applied to CO2 and diol coupling may also find application with other, cyclisation reagents (e.g. carbon sulphide, silanes, carbonyl sulphide etc).Alongside this, studies into novel catalytic systems for polymerisation reactions will be undertaken (organocatalysts and metal complexes), including investigation into switchable catalysts and immobilisation on surfaces for flow applications.