Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst
Density functional theory (DFT) was used to study the regioselectivity of the copolymerization of propylene and the <i>bis</i>-styrenic molecules (DVB and BVPE) using a zirconocene catalyst. This study reveals the following: when hydrogen is introduced to reactivate the catalyst on the v...
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MDPI AG
2022-09-01
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| Online Access: | https://www.mdpi.com/2073-4344/12/9/1039 |
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| author | Shu-Yuan Yu Xiaoxia Peng Fuping Wang Jian Cao Fei Wang Cheng-Gen Zhang |
| author_facet | Shu-Yuan Yu Xiaoxia Peng Fuping Wang Jian Cao Fei Wang Cheng-Gen Zhang |
| author_sort | Shu-Yuan Yu |
| collection | DOAJ |
| description | Density functional theory (DFT) was used to study the regioselectivity of the copolymerization of propylene and the <i>bis</i>-styrenic molecules (DVB and BVPE) using a zirconocene catalyst. This study reveals the following: when hydrogen is introduced to reactivate the catalyst on the vinyl bonds containing DVB or BVPE, the second vinyl bond is inserted into the polymer in a regio-irregular 1,2-way. (I) The 1,2-insertion mode forms more thermodynamically stable products. (II) The 2,1 insertion, DVB-PP<sub>1,</sub> or BVPE-PP<sub>1</sub> needs to rotate 180° along the Zr-C<sub>1</sub> bond to complete the process; thus, it is easier to accomplish the 1,2 insertion. (III) The analysis of the local electrophilicity/nucleophilicity index and the Fukui functions also indicate that the 1,2-insertion mode is the optimal insertion mode. Investigating the mechanism of this experimental phenomenon is important in the development of a functionalization strategy for polypropylene (PP) polymers. |
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| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-10T00:27:41Z |
| publishDate | 2022-09-01 |
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| series | Catalysts |
| spelling | doaj.art-6c4d0617ac2e4977ab59328f662315b22023-11-23T15:31:22ZengMDPI AGCatalysts2073-43442022-09-01129103910.3390/catal12091039Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene CatalystShu-Yuan Yu0Xiaoxia Peng1Fuping Wang2Jian Cao3Fei Wang4Cheng-Gen Zhang5College of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaDensity functional theory (DFT) was used to study the regioselectivity of the copolymerization of propylene and the <i>bis</i>-styrenic molecules (DVB and BVPE) using a zirconocene catalyst. This study reveals the following: when hydrogen is introduced to reactivate the catalyst on the vinyl bonds containing DVB or BVPE, the second vinyl bond is inserted into the polymer in a regio-irregular 1,2-way. (I) The 1,2-insertion mode forms more thermodynamically stable products. (II) The 2,1 insertion, DVB-PP<sub>1,</sub> or BVPE-PP<sub>1</sub> needs to rotate 180° along the Zr-C<sub>1</sub> bond to complete the process; thus, it is easier to accomplish the 1,2 insertion. (III) The analysis of the local electrophilicity/nucleophilicity index and the Fukui functions also indicate that the 1,2-insertion mode is the optimal insertion mode. Investigating the mechanism of this experimental phenomenon is important in the development of a functionalization strategy for polypropylene (PP) polymers.https://www.mdpi.com/2073-4344/12/9/1039copolymerizationregioselectivitychain transfer mechanismzirconocene catalystsDFT calculations |
| spellingShingle | Shu-Yuan Yu Xiaoxia Peng Fuping Wang Jian Cao Fei Wang Cheng-Gen Zhang Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst Catalysts copolymerization regioselectivity chain transfer mechanism zirconocene catalysts DFT calculations |
| title | Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst |
| title_full | Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst |
| title_fullStr | Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst |
| title_full_unstemmed | Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst |
| title_short | Density Functional Theory Study of the Regioselectivity in Copolymerization of <i>bis</i>-Styrenic Molecules with Propylene Using Zirconocene Catalyst |
| title_sort | density functional theory study of the regioselectivity in copolymerization of i bis i styrenic molecules with propylene using zirconocene catalyst |
| topic | copolymerization regioselectivity chain transfer mechanism zirconocene catalysts DFT calculations |
| url | https://www.mdpi.com/2073-4344/12/9/1039 |
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