FI catalysts for olefin polymerization--a comprehensive treatment.

In this perspective, recent developments on palladium and nickel mediated chain walking olefin polymerization and copolymerization with polar functionalized comonomers are described. First, the chain walking polymerization mechanism is discussed followed by its implications in olefin polymerization and copolymerization. Then, recent advances in catalyst design are provided. Special attention is paid to the influence of ligand structures on the catalytic properties. Subsequently, the applications of these chain walking polymerization catalysts in the synthesis of functionalized hyperbranched polymers and copolymers are summarized. Finally, some recent developments and perspectives on very fast and very slow chain walking polymerization catalysts are discussed.

Palladium and Nickel Catalyzed Chain Walking Olefin Polymerization and Copolymerization

A series of sterically demanding α-diimine ligands bearing electron-donating and electron-withdrawing substituents were synthesized by an improved synthetic procedure in high yield. Subsequently, the corresponding Pd complexes were prepared and isolated by column chromatography. These Pd complexes demonstrated unique properties in ethylene polymerization, including high thermal stability and high activity, thus generating polyethylene with a high molecular weight and very low branching density. Similar properties were observed for ethylene/methyl acrylate copolymerization. Because of the high molecular weight and low branching density, the generated polyethylene and ethylene/methyl acrylate copolymer were semicrystalline solids. The (co)polymers had unique microstructures originating from the unique slow-chain-walking activity of these Pd complexes.

Highly Robust Palladium(II) α-Diimine Catalysts for Slow-Chain-Walking Polymerization of Ethylene and Copolymerization with Methyl Acrylate.

Sterically demanding NiII α-diimine precatalysts were synthesized utilizing 2,6-bis(diphenylmethyl)-4-methyl aniline. When activated with methylaluminoxane, the catalyst NiBr2(ArN═C(Me)–C(Me)═NAr) (Ar = 2,6 bis(diphenylmethyl)-4-methylbenzene) was highly active, produced well-defined polyethylene at temperatures up to 100 °C (Mw/Mn = 1.09–1.46), and demonstrated remarkable thermal stability at temperatures appropriate for industrially used gas-phase polymerizations (80–100 °C).

A Robust Ni(II) α-Diimine Catalyst for High Temperature Ethylene Polymerization

The one-pot postfunctionalization allows anchoring a molecular nickel complex into a mesoporous metal-organic framework (Ni@(Fe)MIL-101). It is generating a very active and reusable catalyst for the liquid-phase ethylene dimerization to selectively form 1-butene. Higher selectivity for 1-butene is found using the Ni@(Fe)MIL-101 catalyst than reported for molecular nickel diimino complexes.

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MOF-Supported Selective Ethylene Dimerization Single-Site Catalysts through One-Pot Postsynthetic Modification

On the basis of the strategy of promoting thermostability of α-diimine nickel catalyst by ligand backbone framework, a series of α-diimine nickel(II) complexes with bulky camphyl or diaryl-substituted backbones, [2,6-(R2)2C6H3−N═C(R1)−C(R1)═N−2,6-(R2)2C6H3]NiBr2 (1a, R1 = Ph, R2 = CH3; 2a, R1 = 4-methylphenyl, R2 = CH3; 3a, R1 = 4-fluorophenyl, R2 = CH3; 4a, R1 = camphyl, R2 = CH3; 4b, R1 = camphyl, R2 = i-Pr), were synthesized and used as catalyst precursors for ethylene polymerization. Crystallographic analysis revealed that the bulky camphyl backbone has a valid steric-effect on the nickel center by blocking the axial site for the metal center and suppressing the potential rotation of the CAr−N bond. Ethylene polymerizations catalyzed by these nickel α-diimine complexes activated by MAO were systematically investigated and the influences of the substituted backbones as well as reaction temperature on the catalytic activity, molecular weight and branching structure of the polymers were evaluated. It was...

Thermostable α-Diimine Nickel(II) Catalyst for Ethylene Polymerization: Effects of the Substituted Backbone Structure on Catalytic Properties and Branching Structure of Polyethylene

Substituent Effects of the Backbone in α-Diimine Palladium Catalysts on Homo- and Copolymerization of Ethylene with Methyl Acrylate

An Unsymmetrical Iron(II) Bis(imino)pyridyl Catalyst for Ethylene Polymerization: Effect of a Bulky Ortho Substituent on the Thermostability and Molecular Weight of Polyethylene

Longstanding living polymerization of ethylene: substituent effect on bridging carbon of 2-pyridinemethanamine nickel catalysts

Several N-functionalized bis(phosphanyl)amine ligands respectively containing benzyl, furfuryl, thiophene-2-methyl, thiophene-2-ethyl, and 2-picolyl groups (1a–e) were synthesized and characterized. The ligands reacted with (DME)NiBr2 in CH2Cl2 to give their corresponding nickel complexes [Ph2PN(R)PPh2NiBr2] [R = CH2C6H5 (2a), CH2C4H3O (2b), CH2C4H3S (2c), CH2C5H4N (2d), and CH2CH2C4H3S (2e)]. The structures of these complexes were established by single-crystal X-ray crystallography. All these nickel complexes were highly active towards ethylene oligomerization in the presence of methylaluminoxane or Et2AlCl, producing a high content of butene (C4). Especially for 2e, which contains a thiophene-2-ethyl pendant group, the oligomerization products obtained at –40 °C contained 95.9 mol-% C4 fraction with 100 mol-% 1-butene. Over 50 °C, however, these nickel complexes underwent Friedel–Crafts alkylation of toluene with ethylene and the olefin oligomers.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Syntheses, Structures, and Catalytic Ethylene Oligomerization Behaviors of Bis(phosphanyl)aminenickel(II) Complexes Containing N‐Functionalized Pendant Groups

Lihua Guo

Papers

Thermostable α-Diimine Nickel(II) Catalyst for Ethylene Polymerization: Effects of the Substituted Backbone Structure on Catalytic Properties and Branching Structure of Polyethylene

Substituent Effects of the Backbone in α-Diimine Palladium Catalysts on Homo- and Copolymerization of Ethylene with Methyl Acrylate

An Unsymmetrical Iron(II) Bis(imino)pyridyl Catalyst for Ethylene Polymerization: Effect of a Bulky Ortho Substituent on the Thermostability and Molecular Weight of Polyethylene

Longstanding living polymerization of ethylene: substituent effect on bridging carbon of 2-pyridinemethanamine nickel catalysts

Syntheses, Structures, and Catalytic Ethylene Oligomerization Behaviors of Bis(phosphanyl)aminenickel(II) Complexes Containing N‐Functionalized Pendant Groups