The π–π stacking effect of metallocene catalyst in olefin polymerization

IF 3.1 3区化学 Q2 POLYMER SCIENCE

Polymer Bulletin Pub Date : 2024-07-26 DOI:10.1007/s00289-024-05432-5

Xin Yan, Jianming Yang, Hexin Zhang, Keun-Byoung Yoon, Min Chen

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Abstract

The single-sited metallocene catalyst has attracted significant attention due to its high activity and application in olefin polymerization industry. In this work, we introduced a strategy of in situ modification of metallocene catalyst with pyrene through π–π stacking to study the effect in olefin polymerization. After activated by MMAO, the pyrene-modified metallocene catalyst exhibited high activities (up to 1333 kg mol⁻¹ h⁻¹) in ethylene polymerization, which was 1.9 times higher than that of the pyrene free catalyst system. This could be because the electron-donating ability of cyclopentene to the transition metal was enhanced through π–π interaction of pyrene with cyclopentene. The copolymerization of ethylene and 1-hexene was also studied. The pyrene-modified metallocene catalyst system performs with higher activity in the copolymerization with a lower monomer incorporation ratio. Density functional theory (DFT) calculations indicated the formation of π–π interaction between the Zr center with pyrene molecule leading to the increase in steric hindrance and electron density.

Graphical abstract

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茂金属催化剂在烯烃聚合中的π-π堆积效应

单位茂金属催化剂因其高活性和在烯烃聚合工业中的应用而备受关注。在这项工作中，我们引入了一种通过π-π堆积对茂金属催化剂进行芘原位改性的策略，以研究其在烯烃聚合中的效果。经 MMAO 活化后，芘改性茂金属催化剂在乙烯聚合中表现出较高的活性（高达 1333 kg mol-1 h-1），是无芘催化剂体系的 1.9 倍。这可能是因为芘与环戊烯的π-π相互作用增强了环戊烯对过渡金属的电子供能能力。此外，还研究了乙烯和 1-己烯的共聚。芘改性茂金属催化剂体系在单体掺入率较低的共聚过程中表现出更高的活性。密度泛函理论（DFT）计算表明，Zr 中心与芘分子之间形成了 π-π 相互作用，从而增加了立体阻碍和电子密度。

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来源期刊

Polymer Bulletin 化学-高分子科学

CiteScore

6.00

自引率

6.20%

发文量

审稿时长

5.5 months

期刊介绍： "Polymer Bulletin" is a comprehensive academic journal on polymer science founded in 1988. It was founded under the initiative of the late Mr. Wang Baoren, a famous Chinese chemist and educator. This journal is co-sponsored by the Chinese Chemical Society, the Institute of Chemistry, and the Chinese Academy of Sciences and is supervised by the China Association for Science and Technology. It is a core journal and is publicly distributed at home and abroad. "Polymer Bulletin" is a monthly magazine with multiple columns, including a project application guide, outlook, review, research papers, highlight reviews, polymer education and teaching, information sharing, interviews, polymer science popularization, etc. The journal is included in the CSCD Chinese Science Citation Database. It serves as the source journal for Chinese scientific and technological paper statistics and the source journal of Peking University's "Overview of Chinese Core Journals."