含Salen基团聚合物负载金属催化剂的创制及其羰基化性能研究

Polymer containing Salen ligand supported metal catalysts has become a hot topic in catalytic research, due to the fact that these catalysts combine the advantages of high activity of homogenous metal-Salen catalyst together with the easy separation and better stability of the polymer-supported systems. Taking advantage of diversification and easy modification of Salen ligand, this project is aimed to adopt the strategy of grafting vinyl groups with different aldehydes or amines to design and synthesize polymer containing Salen ligand supported metal catalyst by polymerization method, to develop new catalytic system of oxidative carbonylation of methanol and carbonylative Sonogashira coupling with high activity, high selectivity and recyclability. This new system will provide a clean method to synthesize dimethyl carbonate and α, β-unsaturated alkyne ketone. By taking advantage of advanced characterization methods, the effects of composition and structure of supported catalyst on the reaction activity and recycling properties of carbonylation reactions will be explored, the structure-activity relationships will be revealed.In addition, reaction intermediates will be captured by use of analysis and detection methods, such as ESI-MS, NMR, HRMS, React-IR, etc., which will provide the experimental and theoretical basis for the expanding the application of Salen metal complexes in carbonylation reactions.

含有Salen基团的聚合物负载金属催化剂由于具有均相Salen金属配合物高活性和高分子载体负载金属催化剂易于分离、具有更好的稳定性等优点，成为当前催化研究的热点课题。基于Salen配体结构多样化、易修饰的优点，本项目拟采用烯基接枝于醛、胺侧链的策略，利用聚合方法，设计、合成几类含Salen结构单元的聚合物载体负载金属催化剂；发展高活性、高选择性，易于循环的甲醇氧化羰化、Sonogashira羰化偶联反应新体系，为碳酸二甲酯和α,β-不饱和炔酮的合成提供一条简单清洁的路线。利用表征手段，探讨含有Salen基团的聚合物载体的组成和结构对羰基化反应效果及循环使用性能的影响，揭示构效关系。此外，利用ESI-MS、NMR、HRMS、React-IR等分析测试手段捕获反应中间体，为反应机理的提出提供直接证据，并为拓展Salen金属配合物在羰基化反应中的应用提供实验和理论基础。

含有Salen基团的聚合物负载金属催化剂由于具有均相Salen金属配合物高活性和高分子载体负载金属催化剂易于分离、具有更好的稳定性等优点，成为当前催化研究的热点课题。基于Salen配体结构多样化、易修饰的优点，本课题通过将烯烃基接枝于醛、胺测链的方法，合成了多种含有Salen结构单元的聚合物载体，包括以丙烯酰胺为原料出发经过聚合反应过程得到聚合Salen，以此为载体制备了聚合Salen负载金属催化剂。经过详细的表征确定了催化剂的合成过程、组成组分、微观形貌、表面性质及催化活性中心等，研究polysalen-Pd在Sonogashira羰化偶联反应中及polysalen-Cu在端基炔烃自偶联反应中催化活性及稳定性，揭示了聚合Salen载体对负载金属纳米颗粒活性及稳定性的促进作用，阐明了金属与载体之间的键合关系及反应之间的相关联系，确定了聚合Salen载体在催化反应过程中的配体作用。研究工作较好的完成了计划设定的研究目标，并且在此基础上，随着最新研究结果的发展，进行了进一步的深化和拓展。