Tao Guo , Chuanding Dong , Xiaokai Cheng , Jingdai Wang , Yongrong Yang , Wei Li
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引用次数: 0
Abstract
The ethylene/α-olefin copolymers synthesized by Ziegler-Natta catalysts generally exhibit much higher Short-Chain Branch (SCB) concentration in the low-molecular-weight fraction, which hampers the mechanical properties of the final products. Herein, we investigate the mechanism underlying the origin of SCB distribution at a molecular level. We design a spherical catalyst combining two alcohols with different mobility, after which a second titanation step with incremental TiCl4 loading is applied to drive the migration of alcohol molecules. This migration induces not only the escape of alcohols from the catalyst surface but also the coordination of alcohols with Ti centers, which regulates the mobility of active species on the catalyst surface. We demonstrate that the aggregation behavior of Ti species is directed by their bonding to the MgCl2 surface, where either TiCl3-like clusters or isolated Ti3+ sites can be preferentially synthesized during triethylaluminium activation. Further polymerization results combined with electron paramagnetic resonance analysis show that TiCl3-like clusters and the “dormant” active species contribute to the uniform SCB distribution over different molecular weights, whereas the predominated isolated Ti3+ sites on the MgCl2 (110) plane concentrate the SCB in the low-molecular-weight fraction of the synthesized polyethylene. Taken together, we reveal a correlation between polymer branching distribution and catalytic structures, and show that the latter can be regulated by tailoring the migration of alcohols.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.