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Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst
Density functional theory has been used to elucidate the mechanism of Pd copolymerization of cyclopropenone with ethylene. The results reveal that introducing ethylene and cyclopropenone to Pd catalyst is thermodynamically feasible and generates the α,β-unsaturated ketone unit (UnitA). Cis-mode inse...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9739415/ https://www.ncbi.nlm.nih.gov/pubmed/36501667 http://dx.doi.org/10.3390/polym14235273 |
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author | Zhang, Chenggen Yu, Shuyuan Wang, Fei Wang, Fuping Cao, Jian Zheng, Huimin Chen, Xiaoyu Ren, Aijin |
author_facet | Zhang, Chenggen Yu, Shuyuan Wang, Fei Wang, Fuping Cao, Jian Zheng, Huimin Chen, Xiaoyu Ren, Aijin |
author_sort | Zhang, Chenggen |
collection | PubMed |
description | Density functional theory has been used to elucidate the mechanism of Pd copolymerization of cyclopropenone with ethylene. The results reveal that introducing ethylene and cyclopropenone to Pd catalyst is thermodynamically feasible and generates the α,β-unsaturated ketone unit (UnitA). Cis-mode insertion and Path A(1a) are the most favorable reaction routes for ethylene and cyclopropenone, respectively. Moreover, cyclopropenone decomposition can generate CO in situ without a catalyst or with a Pd catalyst. The Pd-catalyzed decomposition of cyclopropenone exhibits a lower reaction barrier (22.7 kcal/mol) than its direct decomposition. Our study demonstrates that incorporating CO into the Pd catalyst can generate the isolated ketone unit (UnitB). CO is formed first; thereafter, UnitB is generated. Therefore, the total energy barrier of UnitB generation, accounting for the CO barrier, is 22.7 kcal/mol, which is slightly lower than that of UnitA generation (24.0 kcal/mol). Additionally, the possibility of copolymerizing ethylene, cyclopropenone, and allyl acetate (AAc) has been investigated. The free energy and global reactivity index analyses indicate that the cyclopropenone introduction reaction is more favorable than the AAc insertion, which is consistent with the experimental results. Investigating the copolymerization mechanism will help to develop of a functionalization strategy for polyethylene polymers. |
format | Online Article Text |
id | pubmed-9739415 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-97394152022-12-11 Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst Zhang, Chenggen Yu, Shuyuan Wang, Fei Wang, Fuping Cao, Jian Zheng, Huimin Chen, Xiaoyu Ren, Aijin Polymers (Basel) Article Density functional theory has been used to elucidate the mechanism of Pd copolymerization of cyclopropenone with ethylene. The results reveal that introducing ethylene and cyclopropenone to Pd catalyst is thermodynamically feasible and generates the α,β-unsaturated ketone unit (UnitA). Cis-mode insertion and Path A(1a) are the most favorable reaction routes for ethylene and cyclopropenone, respectively. Moreover, cyclopropenone decomposition can generate CO in situ without a catalyst or with a Pd catalyst. The Pd-catalyzed decomposition of cyclopropenone exhibits a lower reaction barrier (22.7 kcal/mol) than its direct decomposition. Our study demonstrates that incorporating CO into the Pd catalyst can generate the isolated ketone unit (UnitB). CO is formed first; thereafter, UnitB is generated. Therefore, the total energy barrier of UnitB generation, accounting for the CO barrier, is 22.7 kcal/mol, which is slightly lower than that of UnitA generation (24.0 kcal/mol). Additionally, the possibility of copolymerizing ethylene, cyclopropenone, and allyl acetate (AAc) has been investigated. The free energy and global reactivity index analyses indicate that the cyclopropenone introduction reaction is more favorable than the AAc insertion, which is consistent with the experimental results. Investigating the copolymerization mechanism will help to develop of a functionalization strategy for polyethylene polymers. MDPI 2022-12-02 /pmc/articles/PMC9739415/ /pubmed/36501667 http://dx.doi.org/10.3390/polym14235273 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Zhang, Chenggen Yu, Shuyuan Wang, Fei Wang, Fuping Cao, Jian Zheng, Huimin Chen, Xiaoyu Ren, Aijin Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst |
title | Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst |
title_full | Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst |
title_fullStr | Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst |
title_full_unstemmed | Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst |
title_short | Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst |
title_sort | density functional theory analysis of the copolymerization of cyclopropenone with ethylene using a palladium catalyst |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9739415/ https://www.ncbi.nlm.nih.gov/pubmed/36501667 http://dx.doi.org/10.3390/polym14235273 |
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