芘环基二亚胺镍催化剂的合成及其乙烯聚合/共聚的性能研究  

Synthesis of Pyrene Basedα-Diimide Nickel Catalysts for Ethylene Polymerization/Copolymerization

作　　者：王文兵 邹陈 陈昶乐 Wen-bing Wang;Chen Zou;Chang-le Chen(Department of Polymer Science and Engineering,University of Science and Technology of China,Hefei 230026)

机构地区：[1]中国科学技术大学高分子科学与工程系,合肥230026

出　　处：《高分子学报》2023年第11期1697-1707,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52203016,U1904212);中国博士后基金(基金号2021M703072,2022T150617);中国科学技术大学统筹推进世界一流大学和一流学科建设专项资金(基金号YD9990002018)资助项目.

摘　　要：选用不同结构的芳香烃基团,可以便捷地设计合成一系列具有不同催化性能的后过渡金属催化剂.芘环芳香烃的结构特征之一是芘环芳香烃分子之间存在π-π堆积作用,因而具有调节过渡金属催化剂性能的潜力.本文设计合成了一系列具有芘环结构的α-二亚胺镍催化剂,利用这些芘环基二亚胺镍催化剂的π-π堆积效应,可使镍催化剂的乙烯聚合活性高达3.12×10^(7)g·mol^(−1)·h^(−1),制备的聚乙烯的重均相对分子质量高达1.98×10^(6)g·mol^(−1).这些催化剂还可以实现乙烯与10-十一烯酸甲酯的共聚,并对有π-π堆积效应的10-十一烯酸芘基酯单体共聚性能更佳.The transition metal catalysts required for coordination polymerization to prepare polyolefins have received high attention from academia and industry with the continuous development of the polyolefin industry.Among them,late transition metal catalysts represented by nickel and palladium have been widely studied in olefin/polar monomer copolymerization reactions due to their low oxygen affinity and high tolerance to polar groups.By selecting aromatic hydrocarbon groups with different structures,a series of late transition metal catalysts with different catalytic properties can be conveniently designed and synthesized.One of the structural characteristics of pyrene ring aromatic hydrocarbons is theπ-πstacking effect between pyrene ring aromatic hydrocarbon molecules,which has the potential to regulate the performance of transition metal catalysts.This article introduced the pyrene ring group into the ligand structure and designed and synthesized a series ofα-diimine nickel catalysts with pyrene ring structure,and the structures of these ligands and catalysts were characterized in detail by nuclear magnetic resonance spectrometer(NMR),electrospray ionization mass spectrometry(ESI-MS),X-ray diffraction(XRD),etc.Subsequently,the ethylene polymerization reaction of these catalysts was studied in heptane solvent.Due to the interaction of pyrene ring groups,theπ-πstacking effect may be formed between these nickel complexes.In addition,adding pyrene molecules to the aggregation system may also form theπ-πstacking effect with the complexes.By utilizing theπ-πstacking effect of these pyrene ring basedα-diimide nickel catalysts,the ethylene polymerization activity of the nickel catalysts was as high as 3.12×10^(7)g·mol^(−1)·h^(−1),with a weight average relative molecular weight of up to 1.98×10^(6)g·mol^(−1)for the prepared polyethylene,and the branching degree of polyethylene was 4-77 C/1000 C.These catalysts can also achieve copolymerization of ethylene with methyl 10-undecanoate,with a copolymerizati

关 键 词：镍催化剂 芘 乙烯聚合 共聚合 聚乙烯 

分 类 号：TQ426[化学工程] TQ325.12