分子模拟研究聚烯烃过渡金属配合物催化剂的聚合活性

项目名称： 分子模拟研究聚烯烃过渡金属配合物催化剂的聚合活性

项目编号： No.21204092

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 高分子科学

项目作者： 杨文泓

作者单位： 中国科学院化学研究所

项目金额： 25万元

中文摘要： 分子模拟方法可以帮助解释配位催化过程中的活性中心和中间体结构、预测催化过程以及产物，具有理论价值和现实意义。然而针对聚烯烃催化剂的催化活性，文献在这方面的报道很少。申请人所在课题组提出利用分子力学与QEq电荷分配相结合的MANCC方法，对部分过渡金属催化剂的催化活性进行了合理的预测与解释。近十年来申请人所在课题组在聚烯烃过渡金属配合物催化剂领域做了广泛的实验研究。本项目将利用MANCC方法对本课题组合成报道的多种催化剂的催化活性展开系统的研究，在模拟实验结果的基础上考察催化剂分子的中心金属类型、配体以及配体上的取代基对催化活性的影响，得出催化剂分子结构与催化活性间定性或定量的关系，获得催化剂调控规律及其理论解释。同时，考察助催化剂以及反应温度等聚合条件对催化活性的影响，探讨变化规律，获得研究结果。帮助指导过渡金属配合物的设计合成，以获得具有温度适应性的高性能聚烯烃催化剂。

中文关键词： 过渡金属配合物；催化活性；DFT计算；定量构效；乙烯聚合

英文摘要： Molecular modeling method is an important tool to investigate the micro structure and property of system at electronic or molecular level, including quantum mechanics, molecular mechanics, molecular dynamics, etc. When applied to research coordination polymerization process, molecular modeling can be employed to predict and explain the active centers and its structure, as well as the catalysis reaction route. Compared to abundent of reports on catalysis mechanism, there are very few literature related to catalysis activity. MANCC method has been developed using the combination of molecular mechanics and QEq charge distribution by the applicant's research group. And this method has been successfully predicted several transition metal complexes precatalyst systems through the revelence of calculated net charge on metal center atom to catalysis activity. Meanwhile, the applicant's research group has been studying the transition metal complexes precatalysts and its polymerization properties for ten years from experimental aspect, containting design, synthesis, preparation, characterization and measurement. In this project, we will investigate diversified complex systems by the MANCC method and compared the calculated results with our experimental data. The main aim of this project is to established the qualitative o

英文关键词： transition metal complex；catalytic activity；DFT calcuation；QSAR；ethylene polymerization