Axial Anagostic Interaction in α-Diimine Nickel Catalysts: An Ultraefficient Occupation Strategy in Suppressing Associative Chain Transfers to Achieve UHMWPEs

IF 5.2 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2025-02-10 DOI:10.1021/acs.macromol.4c03244

Xiaohua Wang, Lishuang Ma, Bo Dong, Chunyu Zhang, Xuequan Zhang, Heng Liu

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Abstract

Axial anagostic bond Mt···H–C can occupy the apical site of d⁸ square planar metal complexes, which is highly desired, yet never explored, for olefin polymerization because of its capability to suppress associative chain transfer to access high molecular weight polyolefin products. In this research, we present a method for how such axial anagostic interaction Ni···H–C can be constructed into α-diimine NiBr₂ complexes, and more importantly, demonstrate its pivotal role in improving the overall ethylene polymerization performance, including (i) ultrahigh efficiency in suppressing associative chain transfer to afford UHMWPEs with M_w up to 724.2 × 10⁴ g/mol, (ii) significantly impeded decomposition of the cationic active species that brings in better storage stability, and (iii) higher branched nature of the PE products that guarantee a well-controlled living fashion for the whole polymerization process even when M_w reaches ultrahigh levels. With the aid of DFT calculations, the nature of such an anagostic bond and its influence on each step of the polymerization process are also elucidated.

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α-二亚胺镍催化剂的轴向解析相互作用：一种抑制结合链转移以获得超高分子量聚乙烯的超高效占领策略

轴向异交键Mt···H-C可以占据d8方形平面金属配合物的顶端位置，这是烯烃聚合非常需要的，但从未被探索过，因为它能够抑制结合链转移以获得高分子量的聚烯烃产品。在本研究中，我们提出了一种如何将这种轴向异向相互作用Ni···H-C构建成α-二亚胺NiBr2配合物的方法，更重要的是，证明了它在提高乙烯聚合整体性能方面的关键作用，包括(i)超高效率地抑制结合链转移，从而提供Mw高达724.2 × 104 g/mol的超高分子量聚乙烯（ii）显著阻碍阳离子活性物质的分解，从而带来更好的储存稳定性。（iii） PE产品具有更高的分支性质，即使在Mw达到超高水平时，也能保证整个聚合过程的良好控制。借助离散傅里叶变换计算，还阐明了这种异交键的性质及其对聚合过程各步骤的影响。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.