Customizing Polyolefin Morphology by Selective Pairing of Alkali Ions with Nickel Phenoxyimine-Polyethylene Glycol Catalysts,Organometallics

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Customizing Polyolefin Morphology by Selective Pairing of Alkali Ions with Nickel Phenoxyimine-Polyethylene Glycol Catalysts
Organometallics ( IF 2.5 ) Pub Date : 2017-11-17 00:00:00 , DOI: 10.1021/acs.organomet.7b00516
Zhongzheng Cai ₁ , Loi H. Do ₁

Affiliation

In the present work, we have prepared nickel phenoxyimine-polyethylene glycol (PEG) catalysts with sterically bulky N-aryl substituents and investigated their ethylene homo- and copolymerization behavior. We have found that different nickel catalyst and alkali ion (Na⁺ or K⁺) combinations yielded polyethylene with different branching microstructures and molecular weights. Our heterobimetallic catalysts can copolymerize ethylene and nonpolar α-olefins with high activity but are strongly inhibited in the presence of polar vinyl olefins. We demonstrate that our heterobimetallic catalysts are significantly more stable in ethylene homopolymerization in comparison to conventional nickel phenoxyimine systems on the basis of time-dependent activity studies. This work showcases the versatility of Lewis acid tunable catalyst constructs to prepare customized polyolefins and suggests that similar design strategies could be applied to other catalyst systems.

中文翻译：

通过碱金属离子与镍苯氧基亚胺-聚乙二醇催化剂的选择性配对来定制聚烯烃的形态

在目前的工作中，我们制备了具有大体积N-芳基取代基的镍苯氧基亚胺-聚乙二醇（PEG）催化剂，并研究了它们的乙烯均聚和共聚行为。我们发现，不同的镍催化剂和碱金属离子（Na ⁺或K ⁺）组合产生具有不同分支微结构和分子量的聚乙烯。我们的杂双金属催化剂可以使乙烯和非极性α-烯烃具有高活性，但在极性乙烯基烯烃的存在下会受到强烈抑制。我们根据时间相关的活性研究证明，与常规的镍苯氧基亚胺体系相比，我们的杂双金属催化剂在乙烯均聚反应中明显更稳定。这项工作展示了路易斯酸可调催化剂构造物在制备定制聚烯烃中的多功能性，并表明类似的设计策略可以应用于其他催化剂体系。

更新日期：2017-11-20

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