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Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction

Polypropylene synthesis is a critical process in the plastics industry, where control of catalytic activity is essential to ensure the quality and performance of the final product. In this study, the effect of two inhibitors, propanol and arsine, on the properties of synthesized polypropylene was in...

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Autores principales: Hernández-Fernández, Joaquín, González-Cuello, Rafael, Ortega-Toro, Rodrigo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10489960/
https://www.ncbi.nlm.nih.gov/pubmed/37688245
http://dx.doi.org/10.3390/polym15173619
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author Hernández-Fernández, Joaquín
González-Cuello, Rafael
Ortega-Toro, Rodrigo
author_facet Hernández-Fernández, Joaquín
González-Cuello, Rafael
Ortega-Toro, Rodrigo
author_sort Hernández-Fernández, Joaquín
collection PubMed
description Polypropylene synthesis is a critical process in the plastics industry, where control of catalytic activity is essential to ensure the quality and performance of the final product. In this study, the effect of two inhibitors, propanol and arsine, on the properties of synthesized polypropylene was investigated. Experiments were conducted using a conventional catalyst to polymerize propylene, and different concentrations of propanol and arsine were incorporated into the process. The results revealed that the addition of propanol led to a significant decrease in the Melt Flow Index (MFI) of the resulting polypropylene. The reduction in the MFI was most notable at a concentration of 62.33 ppm propanol, suggesting that propanol acts as an effective inhibitor by slowing down the polymerization rate and thus reducing the fluidity of the molten polypropylene. On the other hand, introducing arsine as an inhibitor increased the MFI of polypropylene. The maximum increase in the MFI was observed at a concentration of 0.035 ppm arsine. This suggests that small amounts of arsine affect the MFI and Mw of the produced PP. Regarding the catalyst productivity, it was found that as the concentration of propanol in the sample increased (approximately seven ppm), there was a decrease in productivity from 45 TM/kg to 44 TM/kg. Starting from 10 ppm, productivity continued to decline, reaching its lowest point at 52 ppm, with only 35 MT/kg. In the case of arsine, changes in catalyst productivity were observed at lower concentrations than with propanol. Starting from about 0.006 ppm, productivity decreased, reaching 39 MT/kg at a concentration of 0.024 ppm and further decreasing to 36 TM/kg with 0.0036 ppm. Computational analysis supported the experimental findings, indicating that arsine adsorbs more stably to the catalyst with an energy of −60.8 Kcal/mol, compared to propanol (−46.17 Kcal/mol) and isobutyl (−33.13 Kcal/mol). Analyses of HOMO and LUMO orbitals, as well as reactivity descriptors, such as electronegativity, chemical potential, and nucleophilicity, shed light on the potential interactions and chemical reactions involving inhibitors. Generated maps of molecular electrostatic potential (MEP) illustrated the charge distribution within the studied molecules, further contributing to the understanding of their reactivity. The computational results supported the experimental findings and provided additional information on the molecular interactions between the inhibitors and the catalyst, shedding light on the possible modes of inhibition. Solubles in xylene values indicate that both propanol and arsine affect the polymer’s morphology, which may have significant implications for its properties and final applications.
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spelling pubmed-104899602023-09-09 Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction Hernández-Fernández, Joaquín González-Cuello, Rafael Ortega-Toro, Rodrigo Polymers (Basel) Article Polypropylene synthesis is a critical process in the plastics industry, where control of catalytic activity is essential to ensure the quality and performance of the final product. In this study, the effect of two inhibitors, propanol and arsine, on the properties of synthesized polypropylene was investigated. Experiments were conducted using a conventional catalyst to polymerize propylene, and different concentrations of propanol and arsine were incorporated into the process. The results revealed that the addition of propanol led to a significant decrease in the Melt Flow Index (MFI) of the resulting polypropylene. The reduction in the MFI was most notable at a concentration of 62.33 ppm propanol, suggesting that propanol acts as an effective inhibitor by slowing down the polymerization rate and thus reducing the fluidity of the molten polypropylene. On the other hand, introducing arsine as an inhibitor increased the MFI of polypropylene. The maximum increase in the MFI was observed at a concentration of 0.035 ppm arsine. This suggests that small amounts of arsine affect the MFI and Mw of the produced PP. Regarding the catalyst productivity, it was found that as the concentration of propanol in the sample increased (approximately seven ppm), there was a decrease in productivity from 45 TM/kg to 44 TM/kg. Starting from 10 ppm, productivity continued to decline, reaching its lowest point at 52 ppm, with only 35 MT/kg. In the case of arsine, changes in catalyst productivity were observed at lower concentrations than with propanol. Starting from about 0.006 ppm, productivity decreased, reaching 39 MT/kg at a concentration of 0.024 ppm and further decreasing to 36 TM/kg with 0.0036 ppm. Computational analysis supported the experimental findings, indicating that arsine adsorbs more stably to the catalyst with an energy of −60.8 Kcal/mol, compared to propanol (−46.17 Kcal/mol) and isobutyl (−33.13 Kcal/mol). Analyses of HOMO and LUMO orbitals, as well as reactivity descriptors, such as electronegativity, chemical potential, and nucleophilicity, shed light on the potential interactions and chemical reactions involving inhibitors. Generated maps of molecular electrostatic potential (MEP) illustrated the charge distribution within the studied molecules, further contributing to the understanding of their reactivity. The computational results supported the experimental findings and provided additional information on the molecular interactions between the inhibitors and the catalyst, shedding light on the possible modes of inhibition. Solubles in xylene values indicate that both propanol and arsine affect the polymer’s morphology, which may have significant implications for its properties and final applications. MDPI 2023-09-01 /pmc/articles/PMC10489960/ /pubmed/37688245 http://dx.doi.org/10.3390/polym15173619 Text en © 2023 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
Hernández-Fernández, Joaquín
González-Cuello, Rafael
Ortega-Toro, Rodrigo
Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction
title Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction
title_full Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction
title_fullStr Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction
title_full_unstemmed Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction
title_short Parts per Million of Propanol and Arsine as Responsible for the Poisoning of the Propylene Polymerization Reaction
title_sort parts per million of propanol and arsine as responsible for the poisoning of the propylene polymerization reaction
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10489960/
https://www.ncbi.nlm.nih.gov/pubmed/37688245
http://dx.doi.org/10.3390/polym15173619
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