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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...

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Autores principales: Zhang, Chenggen, Yu, Shuyuan, Wang, Fei, Wang, Fuping, Cao, Jian, Zheng, Huimin, Chen, Xiaoyu, Ren, Aijin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
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.
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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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