Semi‐Crystalline Polar Polyethylene: Ester‐Functionalized Linear Polyolefins Enabled by a Functional‐Group‐Tolerant, Cationic Nickel Catalyst

Long, Brian K.; Eagan, James M.; Mulzer, Michael; Coates, Geoffrey W.

doi:10.1002/anie.201601703

Cited by 210 publications

(122 citation statements)

References 104 publications

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“…) . As a note, a related Ni α ‐diimine catalyst containing an unsubstituted dibenzobarrelene backbone was previously reported by Coates and co‐workers, and was shown to polymerize ethylene in a living manner at room temperature . However, Wu and co‐workers recently discovered that by symmetrically substituting the dibenzobarrellene backbone framework with bulky t ‐butyl groups, an even greater enhancement in thermal stability could be realized.…”

Section: Thermally Stable Ni‐ and Pd‐based Catalystsmentioning

confidence: 95%

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Mitchell

Long

2018

Polymer International

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Olefin polymerization catalysts employing late transition metals, such as Ni, Pd, Fe and Co, have been heavily investigated since their discovery in the mid‐1990s. Despite the advantages and appeal these catalysts have displayed in academic research, their implementation in industry has remained restricted due to a variety of limitations and drawbacks. One specific limitation is the relative thermal instability of most late transition metal olefin polymerization catalysts at the temperatures commonly utilized for industrial polymerizations. This review focuses on the development of Ni‐, Pd‐, Fe‐ and Co‐based olefin polymerization catalysts that display increased thermal stability at super‐ambient reaction temperatures. These advances in thermal stability have been realized using a variety of ligand modifications, and their polymerization activities and thermal stability are summarized herein. Lastly, a brief outlook on the future of thermally stable, late transition metal olefin polymerization catalysts is provided. © 2018 Society of Chemical Industry

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Section: Thermally Stable Ni‐ and Pd‐based Catalystsmentioning

confidence: 95%

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Mitchell

Long

2018

Polymer International

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“…This steric effect may be the key factor in the differences between the two sets of catalysts with different connectivity to the naphthalene backbone. [50]. Our groups showed that some sterically very bulky phosphine-sulfonate nickel catalysts could copolymerize ethylene with various polar monomers [51].…”

Section: Pd2" 9 25mentioning

confidence: 97%

Influence of Ligand Backbone Structure and Connectivity on the Properties of Phosphine-Sulfonate Pd(II)/Ni(II) Catalysts

Hong

Pang

et al. 2017

Polymers

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Phosphine-sulfonate based palladium and nickel catalysts have been extensively studied in ethylene polymerization and copolymerization reactions. Previously, the majority of the research works focused on the modifications of the substituents on the phosphorous atom. In this contribution, we systematically demonstrated that the change of the ligand backbone from benzene to naphthalene could greatly improve the properties of this class of catalysts. In the palladium system, this change could increase catalyst stability and polyethylene molecular weights. In the nickel system, this change could dramatically increase the polyethylene molecular weights. Most interestingly, the change in the connectivity of phosphine and sulfonate moieties to the naphthalene backbone could also significantly influence the catalyst properties.

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“…[41] Considering the impressive reactivity of the Brookhart catalysts toward norbornene, [42] and their excellent tolerance toward ester functionalities,C hen and co-workers successfully copolymerized ethylene with polar functionalized norbornenes using a-diimine palladium catalysts. [43,44] Coates and co-workers [45] and Gao and co-workers [46] demonstrated that a-diimine nickel catalysts can mediate ethylene copolymerization with methyl 10-undecenoate.…”

Section: Developments Using the Brookhart And Drent Catalystsmentioning

confidence: 99%

Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers

2019

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Transition‐metal‐catalyzed copolymerization of olefins with polar monomers represents a challenge because of the large variety of substrate‐induced side reactions. However, this approach also holds the potential for the direct synthesis of polar functionalized polyolefins with unique properties. After decades of research, only a few catalyst systems have been found to be suitable for this reaction. Some major advances in catalyst development have been made in the past five years. This Minireview summarizes some of the recent progress in the extensively studied Brookhart and Drent catalyst systems, as well as emerging alternative palladium and nickel catalysts.

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Semi‐Crystalline Polar Polyethylene: Ester‐Functionalized Linear Polyolefins Enabled by a Functional‐Group‐Tolerant, Cationic Nickel Catalyst

Cited by 210 publications

References 104 publications

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Recent advances in thermally robust, late transition metal‐catalyzed olefin polymerization

Influence of Ligand Backbone Structure and Connectivity on the Properties of Phosphine-Sulfonate Pd(II)/Ni(II) Catalysts

Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers

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