α-二亚胺Ni(II)催化剂合成高支化聚乙烯的支链模式、分布及链走机理研究

IF 5.2 1区 化学 Q1 POLYMER SCIENCE
Bohao Peng, Keaton Turney, James Eagan* and Toshikazu Miyoshi*, 
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引用次数: 0

摘要

聚乙烯(PE)的分支数、模式和分布显著地影响着聚乙烯在层次长度尺度上的晶体结构,从而支配着聚乙烯的物理性质。以α-二亚胺镍为催化剂,以单一乙烯为原料合成高支链聚乙烯(HB),每1000个碳有超过100个支链(100b/1kC),但产生复杂的13C溶液态核磁共振波谱。在本研究中,我们在三种镍α-二亚胺催化剂合成的hbpe中分配了许多未分配的13C峰。应用13C化学位移的加性规则,发现了几个新的微观结构。结果成功地揭示了新的分支微观结构,包括(i)成对分支的构型,(ii)连续成对分支和(iii)甲基化分支末端。基于这些新的任务,讨论了hbpe链行走机制的几个见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Branching Pattern, Distribution, and Chain-Walking Mechanism of Highly Branched Polyethylenes Synthesized by α-Diimine Ni(II) Catalysts as Studied via 13C Solution-State NMR Spectroscopy

Branching Pattern, Distribution, and Chain-Walking Mechanism of Highly Branched Polyethylenes Synthesized by α-Diimine Ni(II) Catalysts as Studied via 13C Solution-State NMR Spectroscopy

Branching number, pattern, and distribution of polyethylene (PE) significantly affect the crystalline structures at hierarchical length scales and thus dominate physical properties. Highly branched (HB) PE with over 100 branches per 1000 carbons (100b/1kC) can be synthesized from a sole ethylene feedstock using α-diimine nickel catalysts but results in complex 13C solution-state NMR spectra. In this study, we assign numerous 13C peaks that were unassigned in HBPEs synthesized via three nickel α-diimine catalysts. By application of an additive rule of 13C chemical shifts, several new microstructures are identified. The results successfully reveal new branching microstructures, including (i) the configuration of paired branches, (ii) continual paired branches, and (iii) methylated branch ends. Based on these new assignments, several insights into the chain-walking mechanisms of HBPEs are discussed.

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来源期刊
Macromolecules
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.
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