Olefin Polymerization by Dinuclear Zirconium Catalysts Based on Rigid Teraryl Frameworks: Effects on Tacticity and Copolymerization Behavior
作者:Jessica Sampson、Gyeongshin Choi、Muhammed Naseem Akhtar、E. A. Jaseer、Rajesh Theravalappil、Hassan Ali Al-Muallem、Theodor Agapie
DOI:10.1021/acs.organomet.7b00015
日期:2017.5.22
of bimetallic catalysts for olefin polymerization, a series of structurally related binuclear zirconium catalysts with bisamine bisphenolate and pyridine bisphenolate ligands connected by rigid teraryl units were synthesized. Anthracene-9,10-diyl and 2,3,5,6-tetramethylbenzene-1,4-diyl were employed as linkers. Bulky SiiPr3 and SiPh3 substituents were used in the position ortho to the phenolate oxygen
为了深入了解用于烯烃聚合的双金属催化剂的行为,合成了一系列结构相关的双核锆催化剂,其中双胺双酚盐和吡啶双酚盐配体通过刚性三芳基单元连接。蒽-9,10-二基和2,3,5,6-四甲基苯-1,4-二基用作连接基。在酚盐氧的邻位使用大的Si i Pr 3和SiPh 3取代基。伪Ç小号和Ç 2观察到双胺双酚盐配体的双核配合物存在对称异构体。通常,与单锆类似物相比,双核催化剂显示出更高的全同立构规整度,异构体之间存在一些差异。发现存在双胺胺的双酚盐二锆络合物具有中等活性(最高达1.5 kg mmol Zr –1 h –1),可在存在下将1-己烯聚合为等规富集的聚1-己烯(高达45%mmmm)。化学计量的三苯甲基或苯甲酸硼酸盐活化剂。在生产等规富集聚丙烯的过程中观察到中等活性(最高2.8 kg mmol Zr –1 h –1和最高25.4%mmmm)。先前提出的基于来自第二金属位点的远端空间效应的立构规