Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization
Abstract This quantum chemical study presents the ligand effect and a structure–property relationship in the cationic ring-opening polymerization (CROP) of ε-caprolactone using zirconocene catalysts. We first examined the effects of catalyst structure on the initiation and chain propagation steps of...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-02-01
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| Series: | Scientific Reports |
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| Online Access: | https://doi.org/10.1038/s41598-024-54157-y |
| _version_ | 1827327876367646720 |
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| author | Wijitra Meelua Tanchanok Wanjai Jitrayut Jitonnom |
| author_facet | Wijitra Meelua Tanchanok Wanjai Jitrayut Jitonnom |
| author_sort | Wijitra Meelua |
| collection | DOAJ |
| description | Abstract This quantum chemical study presents the ligand effect and a structure–property relationship in the cationic ring-opening polymerization (CROP) of ε-caprolactone using zirconocene catalysts. We first examined the effects of catalyst structure on the initiation and chain propagation steps of the CROP process. A total of 54 catalyst structures were investigated to understand the influence of the ligand structure on the stability of the catalyst–monomer complex and polymerization activity. The properties of the catalysts were analyzed in terms of ancillary ligands, ligand substituents, and bridging units. Calculations showed that the polymerization follows a proposed cationic mechanism, with ring opening occurring via alkyl-bond cleavage. A correlation between complex stability and activation energy was also observed, with ligand substituents dominating in both steps. While the ancillary ligands directly affect the HOMO energy level, the bridges are mainly responsible for the catalyst geometries, resulting in reduced complex stability and higher activation energy for the propagation step. This study contributes to a better understanding of the structural characteristics of zirconocene catalysts, which offers guidance for improving CROP activities in lactone polymerization. |
| first_indexed | 2024-03-07T15:08:47Z |
| format | Article |
| id | doaj.art-07b608a522be44db9a92280883b7d38f |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-03-07T15:08:47Z |
| publishDate | 2024-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-07b608a522be44db9a92280883b7d38f2024-03-05T18:43:47ZengNature PortfolioScientific Reports2045-23222024-02-0114111310.1038/s41598-024-54157-yComputational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerizationWijitra Meelua0Tanchanok Wanjai1Jitrayut Jitonnom2Demonstration School, University of PhayaoUnit of Excellence in Computational Molecular Science and Catalysis, and Division of Chemistry, School of Science, University of PhayaoUnit of Excellence in Computational Molecular Science and Catalysis, and Division of Chemistry, School of Science, University of PhayaoAbstract This quantum chemical study presents the ligand effect and a structure–property relationship in the cationic ring-opening polymerization (CROP) of ε-caprolactone using zirconocene catalysts. We first examined the effects of catalyst structure on the initiation and chain propagation steps of the CROP process. A total of 54 catalyst structures were investigated to understand the influence of the ligand structure on the stability of the catalyst–monomer complex and polymerization activity. The properties of the catalysts were analyzed in terms of ancillary ligands, ligand substituents, and bridging units. Calculations showed that the polymerization follows a proposed cationic mechanism, with ring opening occurring via alkyl-bond cleavage. A correlation between complex stability and activation energy was also observed, with ligand substituents dominating in both steps. While the ancillary ligands directly affect the HOMO energy level, the bridges are mainly responsible for the catalyst geometries, resulting in reduced complex stability and higher activation energy for the propagation step. This study contributes to a better understanding of the structural characteristics of zirconocene catalysts, which offers guidance for improving CROP activities in lactone polymerization.https://doi.org/10.1038/s41598-024-54157-yCatalyst designLactoneZirconocenePolymerization catalystDensity functional theory |
| spellingShingle | Wijitra Meelua Tanchanok Wanjai Jitrayut Jitonnom Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization Scientific Reports Catalyst design Lactone Zirconocene Polymerization catalyst Density functional theory |
| title | Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization |
| title_full | Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization |
| title_fullStr | Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization |
| title_full_unstemmed | Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization |
| title_short | Computational evaluation of zirconocene catalysts for ε-caprolactone cationic ring-opening polymerization |
| title_sort | computational evaluation of zirconocene catalysts for ε caprolactone cationic ring opening polymerization |
| topic | Catalyst design Lactone Zirconocene Polymerization catalyst Density functional theory |
| url | https://doi.org/10.1038/s41598-024-54157-y |
| work_keys_str_mv | AT wijitrameelua computationalevaluationofzirconocenecatalystsforecaprolactonecationicringopeningpolymerization AT tanchanokwanjai computationalevaluationofzirconocenecatalystsforecaprolactonecationicringopeningpolymerization AT jitrayutjitonnom computationalevaluationofzirconocenecatalystsforecaprolactonecationicringopeningpolymerization |