Advance on nickel‐ and <scp>palladium‐catalyzed</scp> insertion copolymerization of ethylene and acrylate monomers

Zheng, Handou; Qiu, Zonglin; Li, Donghui; Pei, Lixia; Gao, Haiyang

doi:10.1002/pol.20230389

Cited by 12 publications

(9 citation statements)

References 166 publications

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“…The produced EMA copolymers have a chain structure very similar to that of industrial EMA made by free radical polymerization, although industrial EMA has a much higher MA content. The lightly branched EMA with in-chain and terminal MA units was not prepared using previously reported nickel and palladium catalysts, such as α-diimine palladium catalysts (highly branched EMA with terminal MA) as well as phosphine-sulfonato palladium catalysts and phosphino-phenolato nickel catalysts (fully linear EMA with in-chain MA). , …”

Section: Resultsmentioning

confidence: 99%

“…The lightly branched EMA with in-chain and terminal MA units was not prepared using previously reported nickel and palladium catalysts, such as α-diimine palladium catalysts (highly branched EMA with terminal MA) as well as phosphinesulfonato palladium catalysts and phosphino-phenolato nickel catalysts (fully linear EMA with in-chain MA). 64,65 Theoretical DFT Study. To better understand the role of Ni−phenyl interactions in promoting E/MA copolymerization, a comprehensive theoretical DFT study for Ni-Me was performed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

Zheng,

Qiu,

Gao

et al. 2024

Macromolecules

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As a widely used functional polyolefin, the industrial ethylene (E)-methyl acrylate (MA) copolymer (EMA), prepared by free radical polymerization under harsh conditions, is a lightly branched copolymer with in-chain and terminal MA incorporation. Metal-catalyzed E/MA copolymerization as an alternative polymerization technique is highly attractive and challenging. Herein, we first report efficient direct E/MA copolymerization using "sandwich" dibenzobarrelene-derived α-diimine nickel catalysts. The produced lightly branched EMA copolymers with in-chain, pendant, and terminal MA units have a chain structure very similar to industrial EMA, which is not prepared using the previously reported nickel and palladium catalysts. Experimental results support that noncovalent Ni−phenyl interactions in α-diimine nickel catalysts promote E/MA copolymerization. Density functional theory studies clearly illuminate the crucial role of Ni− phenyl interactions in E/MA copolymerization and well explain the formation of in-chain, pendant, and terminal MA units in the EMA copolymer chain.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

Zheng,

Qiu,

Gao

et al. 2024

Macromolecules

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“…Although Pd-based catalyst systems have demonstrated robust reactivity for a number of polar functional comonomers, − ,− the inherent high cost of Pd is one of the drawbacks to the adoption of this technology commercially. Alternatively, the use of Ni-based catalysts offers a more cost-effective solution for copolymerizing ethylene and polar functional comonomers.…”

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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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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“…Owing to their weak electrophilicity and oxophilicity, Ni and Pd catalysts enable the direct copolymerization of ethylene with both fundamental polar monomers and special polar monomers [ 27 , 28 , 29 ]. Most related studies have focused on the use of Pd catalysts [ 30 , 31 ]. Compared to Ni catalysts bearing similar ligand structures, Pd catalysts typically demonstrate better tolerance towards polar groups.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Nickel Catalysts with Industrial Exploitability for Copolymerization of Ethylene with Polar Monomers

Wang,

Lai,

Gao

et al. 2024

Polymers

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The direct copolymerization of ethylene with polar monomers to produce functional polyolefins continues to be highly appealing due to its simple operation process and controllable product microstructure. Low-cost nickel catalysts have been extensively utilized in academia for the synthesis of polar polyethylenes. However, the development of high-temperature copolymerization catalysts suitable for industrial production conditions remains a significant challenge. Classified by the resultant copolymers, this review provides a comprehensive summary of the research progress in nickel complex catalyzed ethylene-polar monomer copolymerization at elevated temperatures in the past five years. The polymerization results of ethylene–methyl acrylate copolymers, ethylene-tert–butyl acrylate copolymers, ethylene–other fundamental polar monomer copolymers, and ethylene–special polar monomer copolymers are thoroughly summarized. The involved nickel catalysts include the phosphine-phenolate type, bisphosphine-monoxide type, phosphine-carbonyl type, phosphine-benzenamine type, and the phosphine-enolate type. The effective modulation of catalytic activity, molecular weight, molecular weight distribution, melting point, and polar monomer incorporation ratio by these catalysts is concluded and discussed. It reveals that the optimization of the catalyst system is mainly achieved through the methods of catalyst structure rational design, extra additive introduction, and single-site catalyst heterogenization. As a result, some outstanding catalysts are capable of producing polar polyethylenes that closely resemble commercial products. To achieve industrialization, it is essential to further emphasize the fundamental science of high-temperature copolymerization systems and the application performance of resultant polar polyethylenes.

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Advance on nickel‐ and palladium‐catalyzed insertion copolymerization of ethylene and acrylate monomers

Cited by 12 publications

References 166 publications

Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

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

Recent Advances in Nickel Catalysts with Industrial Exploitability for Copolymerization of Ethylene with Polar Monomers

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