Unraveling the Reactivity of SiO 2 -Supported Nickel Catalyst in Ethylene Copolymerization with Polar Monomers: A Theoretical Study.
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| Title: | Unraveling the Reactivity of SiO 2 -Supported Nickel Catalyst in Ethylene Copolymerization with Polar Monomers: A Theoretical Study. |
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| Authors: | Ortega, Daniela E.1 (AUTHOR) daniela.ortega@ubo.cl, Cortés-Arriagada, Diego2 (AUTHOR) |
| Source: | Polymers (20734360). May2025, Vol. 17 Issue 9, p1268. 20p. |
| Subjects: | Nickel catalysts, Catalyst selectivity, Heterogeneous catalysts, Vinyl polymers, Catalyst supports |
| Abstract: | Understanding the catalytic behavior of heterogeneous systems for the copolymerization of ethylene with polar monomers is essential for developing advanced functional polyolefins. In this study, we conducted a quantum chemical investigation of the SiO2-supported Ni–allyl–α-imine ketone catalyst (Ni-OH@SiO2) to uncover the factors governing monomer insertion, selectivity, and reactivity. Using DFT calculations and energy decomposition analysis (ALMO-EDA), we evaluated the coordination and insertion of six industrially relevant polar monomers, comparing their behavior to ethylene homopolymerization. Our results show that special polar monomers (SPMs) with aliphatic spacers, such as vinyltrimethoxysilane (vTMS) and 5-hexenyl acetate (AMA), exhibit favorable insertion profiles due to enhanced electrostatic and orbital interactions with minimal steric hindrance. In contrast, fundamental polar monomers (FPMs), including methyl acrylate (MA) and vinyl chloride (vCl), show higher activation barriers and increased Pauli repulsion due to strong electron-withdrawing effects and conjugation with the vinyl group. AMA displayed the lowest activation barrier (7.4 kcal/mol) and highest insertion thermodynamic stability (−17.6 kcal/mol). These findings provide molecular-level insight into insertion mechanisms and comonomer selectivity in Ni–allyl catalysts supported on silica, extending experimental understanding. This work establishes key structure–reactivity relationships and offers design principles for developing efficient Ni-based heterogeneous catalysts for polar monomer copolymerization. [ABSTRACT FROM AUTHOR] |
| Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
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| Header | DbId: egs DbLabel: Engineering Source An: 185127540 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Unraveling the Reactivity of SiO 2 -Supported Nickel Catalyst in Ethylene Copolymerization with Polar Monomers: A Theoretical Study. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Ortega%2C+Daniela+E%2E%22">Ortega, Daniela E.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> daniela.ortega@ubo.cl</i><br /><searchLink fieldCode="AR" term="%22Cortés-Arriagada%2C+Diego%22">Cortés-Arriagada, Diego</searchLink><relatesTo>2</relatesTo> (AUTHOR) – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. May2025, Vol. 17 Issue 9, p1268. 20p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Nickel+catalysts%22">Nickel catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Catalyst+selectivity%22">Catalyst selectivity</searchLink><br /><searchLink fieldCode="DE" term="%22Heterogeneous+catalysts%22">Heterogeneous catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Vinyl+polymers%22">Vinyl polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Catalyst+supports%22">Catalyst supports</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Understanding the catalytic behavior of heterogeneous systems for the copolymerization of ethylene with polar monomers is essential for developing advanced functional polyolefins. In this study, we conducted a quantum chemical investigation of the SiO2-supported Ni–allyl–α-imine ketone catalyst (Ni-OH@SiO2) to uncover the factors governing monomer insertion, selectivity, and reactivity. Using DFT calculations and energy decomposition analysis (ALMO-EDA), we evaluated the coordination and insertion of six industrially relevant polar monomers, comparing their behavior to ethylene homopolymerization. Our results show that special polar monomers (SPMs) with aliphatic spacers, such as vinyltrimethoxysilane (vTMS) and 5-hexenyl acetate (AMA), exhibit favorable insertion profiles due to enhanced electrostatic and orbital interactions with minimal steric hindrance. In contrast, fundamental polar monomers (FPMs), including methyl acrylate (MA) and vinyl chloride (vCl), show higher activation barriers and increased Pauli repulsion due to strong electron-withdrawing effects and conjugation with the vinyl group. AMA displayed the lowest activation barrier (7.4 kcal/mol) and highest insertion thermodynamic stability (−17.6 kcal/mol). These findings provide molecular-level insight into insertion mechanisms and comonomer selectivity in Ni–allyl catalysts supported on silica, extending experimental understanding. This work establishes key structure–reactivity relationships and offers design principles for developing efficient Ni-based heterogeneous catalysts for polar monomer copolymerization. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.3390/polym17091268 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 20 StartPage: 1268 Subjects: – SubjectFull: Nickel catalysts Type: general – SubjectFull: Catalyst selectivity Type: general – SubjectFull: Heterogeneous catalysts Type: general – SubjectFull: Vinyl polymers Type: general – SubjectFull: Catalyst supports Type: general Titles: – TitleFull: Unraveling the Reactivity of SiO 2 -Supported Nickel Catalyst in Ethylene Copolymerization with Polar Monomers: A Theoretical Study. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Ortega, Daniela E. – PersonEntity: Name: NameFull: Cortés-Arriagada, Diego IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 05 Text: May2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 20734360 Numbering: – Type: volume Value: 17 – Type: issue Value: 9 Titles: – TitleFull: Polymers (20734360) Type: main |
| ResultId | 1 |
