Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework
Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework
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DOI：
10.1021/jacs.6b05200
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发表时间：
2016-08-17
影响因子：
15
通讯作者：
Dinca, Mircea
中科院分区：
文献类型：
--
作者：
Comito, Robert J.;Fritzsching, Keith J.;Dinca, Mircea
单点非均相催化剂的发展使先进聚烯烃的制造成为可能。金属有机骨架（MOFs）作为一种具有巨大潜力的非均相催化剂，可以在分子水平上进行设计和调整。在这项工作中，锌的交换。离子在Zn5CL4(BTDD)（3), H2BTDD = bis（1H1,2,3-三唑[4,5-b],[4',5' i]）二苯二氮[1,4]二恶英）（MF U-4l）中与活性金属的反应建立了一个在高表面积固体中选择性烯烃聚合的通用平台，有望用于工业催化。由这些材料制备的聚乙烯的表征显示了分子和形态的控制。值得注意的是，反应性接近单位点催化剂，证明了低多分散性指数和良好的分子量控制。我们进一步证明了三种新的催化剂能使乙烯和丙烯共聚。聚合物在催化剂周围均匀生长。文章提供了一种控制聚合物形态的机制，这是连续流动过程的相关度量。
The manufacture of advanced polyolefins has been critically enabled by the development of single-site -heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc. ions in Zn5CL4(BTDD)(3), H2BTDD = bis(1H1,2,3-triazolo [4,5-b],[4',5' i])diberizo[1,4] dioxin) (MF U-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological, control. Notably, reactivity approaches single-site catalysfs, evidenced by low polydispersity indices, and good molecular weight control. We, further show that thee new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst. articles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes.