Controlled Polymerization in Polar Solvents to Ultrahigh Molecular Weight Polyethylene

Kenyon, Philip; Wörner, Melissa; Mecking, Stefan

doi:10.1021/jacs.8b03223

Cited by 108 publications

(95 citation statements)

References 35 publications

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“…The ability of complexes Ni4 and Ni-OH to generate UHMWPE is quite surprising considering their sterically open characteristics. The synthesis of UHMWPE using nickel catalysts remains challenging, and very few nickel systems have these capabilities [64][65][66][67][68][69][70] . Furthermore, it is even more challenging to develop heterogeneous nickel catalyst with such capabilities, and to the best of our knowledge, this type of system has not been reported previously.…”

Section: Ni-nimentioning

confidence: 99%

A simple and versatile nickel platform for the generation of branched high molecular weight polyolefins

2020

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The development of high-performance transition metal catalysts has long been a major driving force in academic and industrial polyolefin research. Late transition metal-based olefin polymerization catalysts possess many unique properties, such as the ability to generate variously branched polyolefins using only ethylene as the feedstock and the capability of incorporating polar functionalized comonomers without protecting agents. Here we report the synthesis and (co)polymerization studies of a simple but extremely versatile α-iminoketone nickel system. This type of catalyst is easy to synthesize and modify, and it is thermally stable and highly active during ethylene polymerization without the addition of any cocatalysts. Despite the sterically open nature, these catalysts can generate branched Ultra-High-Molecular-Weight polyethylene and copolymerize ethylene with a series of polar comonomers. The versatility of this platform has been further demonstrated through the synthesis of a dinuclear nickel catalyst and the installation of an anchor for catalyst heterogenization.

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Section: Ni-nimentioning

confidence: 99%

A simple and versatile nickel platform for the generation of branched high molecular weight polyolefins

2020

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“…[74,77,78] Although significant effort has been devoted to this research area, state-of-the-art phosphine sulfonate (and related) palladium complexes produce materials of low molecular weight, realize only moderate functional group incorporation, and lack sufficient catalytic activities for industrial applications. [79][80][81][82] Post-polymerization modification of polyolefins transforms these high-volume and low-cost commodity polymers into value-added materials.The foundational challenge of this approach is the need to selectively functionalize unactivated CÀHbonds.T his compelling problem has led to anumber of contemporary approaches for the selective CÀHf unctionalization of polyolefins.B oaen and Hillmyer previously reviewed this area;t hus,t his section will focus primarily on work conducted since 2005. [75] Metal-catalyzed methods for the CÀHfunctionalization of complex small-molecule substrates have been the subject of numerous recent reports.…”

Section: Polyolefinsmentioning

confidence: 99%

“…Late‐transition‐metal catalysts, which are generally more tolerant to polar functional groups, have shown promise . Although significant effort has been devoted to this research area, state‐of‐the‐art phosphine sulfonate (and related) palladium complexes produce materials of low molecular weight, realize only moderate functional group incorporation, and lack sufficient catalytic activities for industrial applications …”

Section: Polyolefinsmentioning

confidence: 99%

C−H Functionalization of Commodity Polymers

et al. 2019

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Synthetic manipulation of polymer substrates is one of the oldest and most reliable methods to increase the functional diversity of soft materials. Modifying the chemical structure of polymers that are already produced on a commodity scale leverages the current high‐volume and low‐cost production of commodity plastics for the discovery of modern materials. A myriad of polymer C−H functionalization methods have been developed which enable the modification of material properties on both a laboratory and industrial scale. More recently, driven by advances in C−H activation, photoredox catalysis, and radical chemistry, chemoselective approaches have emerged as a means to impart precise functionality onto commodity polymer substrates. This Review discusses the historical significance of and contemporary advances in the C−H functionalization of commodity polymers. The conceptual approach outlined herein presents exciting new directions for the field, including increasing the value of otherwise pervasive materials, uncovering entirely new material properties, and a viable path to upcycle post‐consumer plastic waste.

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“…Katalysatoren mit späten Übergangsmetallen, die in der Regel toleranter gegenüber einer polaren funktionellen Gruppe sind, haben sich als vielversprechend erwiesen . Trotz erheblicher Bemühungen auf diesem Forschungsgebiet erbringen Phosphinsulfonat und damit verbundene Palladiumkomplexe nach dem Stand der Technik nur Materialien von geringem Molekulargewicht, bewirken nur einen moderaten Einbau von funktionellen Gruppen und zeigen keine ausreichende katalytische Aktivität für die industrielle Anwendung …”

Section: Polyolefineunclassified

C‐H‐Funktionalisierung von Standardpolymeren

et al. 2019

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Die präparative Modifizierung von Polymersubstraten ist eine der ältesten und zuverlässigsten Methoden zur Erhöhung der funktionellen Vielfalt von weichen Materialien. Bei der Modifizierung der chemischen Struktur von Polymeren, die bereits in großem Maßstab hergestellt werden, wird die jetzige kostengünstige Massenproduktion von Standardkunststoffen für die Erschließung moderner Materialien genutzt. Es wurden unzählige Methoden zur C‐H‐Funktionalisierung von Polymeren entwickelt, die die Modifizierung von Materialeigenschaften sowohl im Labormaßstab als auch im industriellen Maßstab ermöglichen. Vorangetrieben durch Fortschritte bei der C‐H‐Aktivierung, in der Photoredoxkatalyse und in der Radikalchemie, haben sich in letzter Zeit chemoselektive Methoden zu einem Weg entwickelt, um Standardpolymersubstraten eine bestimmte Funktionalität zu verleihen. Dieser Aufsatz erörtert die historische Bedeutung und die aktuellen Fortschritte der C‐H‐Funktionalisierung von Standardpolymeren. Der konzeptionelle Ansatz, über den hier ein Überblick gegeben wird, verspricht interessante neue Entwicklungsrichtungen für das Gebiet, einschließlich der Erhöhung des Wertes von überall vorhandenen Materialien, der Entdeckung vollkommen neuer Materialeigenschaften und der Einführung eines gangbaren Weges für das Upcycling von nach Gebrauch anfallenden Kunststoffabfällen.

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Controlled Polymerization in Polar Solvents to Ultrahigh Molecular Weight Polyethylene

Cited by 108 publications

References 35 publications

A simple and versatile nickel platform for the generation of branched high molecular weight polyolefins

A simple and versatile nickel platform for the generation of branched high molecular weight polyolefins

C−H Functionalization of Commodity Polymers

C‐H‐Funktionalisierung von Standardpolymeren

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