Synthesis of UHMWPE by neutral phosphine-phenolate based nickel catalysts

Peng, Dan; He, Hong; Pang, Wenmin; Behzadi, Shabnam; Qasim, Muhammad

doi:10.1016/j.polymer.2023.126019

Cited by 5 publications

(2 citation statements)

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“…It has been shown that the [P,O] 1,4-chelate ligand framework is privileged for Ni and Pd catalysts for ethylene/polar monomer copolymerization. The ability of SHOP-type nickel catalysts to incorporate polar functional monomers and achieve high M w polymers has been enhanced by increased steric bulk and, more recently, hemilabile donors, such as −OMe substituents on the aryl groups of the phosphine moiety. , Additionally, catalyst performance can be modulated via steric modifications on the “O” side of the ligand (R 1 substituent, Figure ) to increase the incorporation of acrylate . Cationic analogs of the SHOP ligand framework ( B , Figure ), originally reported by Brookhart and colleagues, have been demonstrated to be highly active polymerization catalysts that achieve increased M w compared to the traditional SHOP catalyst .…”

Section: Introductionmentioning

confidence: 99%

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Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization

Rivet,

Henderson,

Marshall

et al. 2024

Organometallics

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Phosphine–imidate-supported nickel catalysts were synthesized and tested for ethylene/acrylate copolymerization activity. Phosphine–amide metalation studies with (pyridine)2Ni(CH2Si(CH3)3)2 (py2Ni(CH2TMS)2) suggest that the metalation proceeds via an intermediate phosphine–amide complex ([P,O–amide]Ni(CH2TMS)2). Subsequent deprotonation of the amide N–H gives access to the phosphine–imidate-supported nickel complex ([P,O–imidate]pyNi(CH2TMS)). The imidate form of the ligand proved to be critical for polymerization activity. The phosphine–imidate nickel catalysts described herein were capable of producing ethylene/acrylate copolymers with molecular weights (M w) from 700 to 120,000 g/mol and with acrylate incorporation >2.6 mol % in some cases. It was determined that hemilabile alkoxy groups on the phosphine aryl groups were necessary to achieve high M w and acrylate incorporation. These results demonstrate that phosphine–amides, a well-studied ligand class, can be utilized in the imidate form to access highly active neutral nickel polymerization catalysts.

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Section: Introductionmentioning

confidence: 99%

“…This has been the motivation for the significant growth in this area in recent years. As a result, several substantial improvements have been made in catalyst stability and copolymerization activity in the presence of a variety of polar functional groups. − ,− …”

Section: Introductionmentioning

confidence: 99%

Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization

Rivet,

Henderson,

Marshall

et al. 2024

Organometallics

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Enhancing Suppression of Chain Transfer via Installing Bulky N‐ortho‐Aryl Substituents into α‐Diimine Nickel System

Ma,

Nie,

Pang

et al. 2024

ChemCatChem

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Recently, the important role of sterically bulky aromatic substituents at the axial position of the metal center for synthesizing high‐performance catalysts were recognized. In this study, a series of α‐diimine nickel complexes with bulky N‐ortho‐aryl substituents were designed and synthesized. The as‐synthesized nickel complexes showed high activities (up to 2.3×107 g·mol‐1·h‐1) and superior thermostability, giving access to moderately branched polyethylenes (35‐86/1000C) with high molecular weights (up to 197.5×104 g·mol‐1). The polyethylene materials generated by these nickel complexes at 80 °C exhibited outstanding tensile mechanical. In addition, these nickel complexes could also catalyze the copolymerization of ethylene and polar monomer with modest activity (such as undecenoic acid, 10‐undecen‐1‐ol and 6‐chlorohex‐1‐ene), yielding functionalized polyolefin with adjustable molecular weights (6.8‐222.9×104 g·mol‐1) and incorporation ratios (0.2‐4.3 mol%).

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Ethylene homo and co‐polymerization catalyzed by extensively bulky nickel catalysts with shielding wings of chlorine atoms

Ahmad,

Wang,

Tian

et al. 2024

Journal of Polymer Science

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Designing the catalysts to get high molecular weight polyethylene is an art. The catalysts bearing imine functionality derived from 8‐arylnaphthyl amines are more impressive and attractive in this regard. In this work, we synthesize 2,4‐dibenzhydryl‐8‐(3,5‐dichlorophenyl)naphthalen‐1‐amine to condense with picolinaldehyde, pyridine‐N‐oxide‐2‐carbaldehyde and 3,4‐dibutanone and then subsequently the treatment of resulting ligands with nickel precursors to get the corresponding catalysts. It was hypothesized that 3,5‐dichlorophenyl having extended wings of chlorine atoms along with bulky dibenzhydryl groups can provide good shielding on both apical positions of metal in response to slow down the chain transfer. More interestingly, the polymerization was done in industrially claimed n‐heptane solvent. All the catalysts showed activity in an order of 106, whereas a value of 1.04 × 107 g mol−1 h−1 has been recorded from keto‐imine based Ni‐3 catalyst. All catalysts generates polymer with high molecular weight with maximum value was recorded by Ni‐2 up to 37.4 × 104 g mol−1. Ni‐3 can also incorporate methyl 10‐undecenoate up to 2.6% in polyethylene backbone.

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Synthesis of UHMWPE by neutral phosphine-phenolate based nickel catalysts

Cited by 5 publications

References 53 publications

Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization

Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization

Enhancing Suppression of Chain Transfer via Installing Bulky N‐ortho‐Aryl Substituents into α‐Diimine Nickel System

Ethylene homo and co‐polymerization catalyzed by extensively bulky nickel catalysts with shielding wings of chlorine atoms

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