开发新型双齿和三齿氮配体在后过渡金属催化乙烯聚合反应的研究

Polyethylene (PE) resin is one of the most important polymer materials. However, the domestic situation is that low-middle valued resins are over-manufactured, but lack of high valued ones. This situation has not been significantly improved because of the core intellectual property problems of the polymerization catalysts and/or polymerization processes. Fortunately, the appearance of the late-transition-metal catalyzed ethylene polymerization provides an opportunity to change the situation. Our previous researches on the late-transition-metal complexes, which their nitrogen-base ligands were derived the backbones of hydroquilinone and its analogs, showed their catalytic efficiency and activity. Based on the preliminary results, in this project, we plan to design and synthesize more novel bidentate and tridentate nitrogen-base ligands from the backbones of hydroquilinone and its analogs to modify the structures of both electronic property and steric property. These newly developed ligands will be formed to their corresponding late-transition-metal complexes, which would be served as the catalysts in the catalytic ethylene polymerization. It hopes that the new catalyst systems could achieve some breakthrough on the thermostability and catalytic property, furthermore, the high performance of PE resin. On the integration of the relationship between the ligand structure and the microstructure of polymer, we are able to improve the catalytic efficency and the polymeric process, and finally, high performance PE resins with the self-owned intellectual property are highly expected.

聚乙烯树脂是高分子材料产业中最重要的组成部分。但是目前国内的现状是中低档树脂过剩而高档树脂短缺。由于催化剂和聚合工艺的核心知识产权问题，这个状况还在持续。后过渡金属配合物催化剂催化的聚乙烯的研究是改变这一状况的一个机会。之前我们以氢化喹啉酮及其类似物为氮配体骨架开发的后过渡金属催化剂在聚乙烯反应研究中获得了初步结果，在此基础上，本项目进一步设计新型的双齿和三齿氮配体的结构，期望在电子性能和空间结构方面修饰和改进后催化剂在乙烯聚合反应中，能够在耐热稳定性能、催化活性方面取得突破，并获得高性能聚烯烃树脂。在不断总结配体结构与聚合物微结构之间的关系，提升催化剂的催化效率和乙烯聚合反应的工艺，期望实现拥有自主知识产权的高性能的聚乙烯树脂。

聚乙烯树脂是高分子材料产业中最重要的组成部分，国内的现状是中低档树脂过剩而高档树脂短缺。在乙烯聚合反应中国内缺乏催化剂和聚合工艺等核心知识产权，而后过渡金属配合物催化剂催化的聚乙烯领域有机会改变这一状况。我们在氢化喹啉酮为骨架开发的后过渡金属催化剂在聚乙烯反应研究中获得了初步结果的基础上，本项目的实施，在配体骨架上进行了改造，并衍生了新型的双齿和三齿氮配体，进一步与后过渡金属形成的催化剂体系。在乙烯聚合反应中作为催化剂，成功地实现了几个突破。双齿氮Ni配合物在乙烯齐聚方面获得较好的结果；或具有低分子量、窄分布、高支化度且潜在官能化的特点的聚乙烯；三齿氮Fe催化剂在热稳定性和催化性能上都接近了工业化的要求，尤其获得了高性能的聚乙烯蜡产物。研究结果在电子性能和空间结构方面的规律性认识对进一步设计配体结构具有指导意义。还有大位阻双齿氮配体的Pd配合物在偶联反应、还原Heck反应、炔烃氢芳基化反应中也表现了极好的催化性能。