Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties
The study focused on the evaluation of the influence of inhibitory compounds such as hydrogen sulfide (H2S) and methanol (CH3OH) on the catalytic productivity and properties of the polymers in the polymerization process with the Ziegler–Natta catalyst. The investigation involved experimental measure...
- Autores:
-
Hernández Fernández, Joaquín
González Cuello, Rafael
Ortega Toro, Rodrigo
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2023
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/13674
- Acceso en línea:
- https://hdl.handle.net/11323/13674
https://repositorio.cuc.edu.co/
- Palabra clave:
- Ziegler–Natta polymerization
Hydrogen sulfide
Methanol
Catalyst productivity
Molecular weight
Melt flow index
Xylene solubility
DFT calculations
Reactivity descriptors
- Rights
- openAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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| dc.title.eng.fl_str_mv |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| title |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| spellingShingle |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties Ziegler–Natta polymerization Hydrogen sulfide Methanol Catalyst productivity Molecular weight Melt flow index Xylene solubility DFT calculations Reactivity descriptors |
| title_short |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| title_full |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| title_fullStr |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| title_full_unstemmed |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| title_sort |
Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer properties |
| dc.creator.fl_str_mv |
Hernández Fernández, Joaquín González Cuello, Rafael Ortega Toro, Rodrigo |
| dc.contributor.author.none.fl_str_mv |
Hernández Fernández, Joaquín González Cuello, Rafael Ortega Toro, Rodrigo |
| dc.subject.proposal.eng.fl_str_mv |
Ziegler–Natta polymerization Hydrogen sulfide Methanol Catalyst productivity Molecular weight Melt flow index Xylene solubility DFT calculations Reactivity descriptors |
| topic |
Ziegler–Natta polymerization Hydrogen sulfide Methanol Catalyst productivity Molecular weight Melt flow index Xylene solubility DFT calculations Reactivity descriptors |
| description |
The study focused on the evaluation of the influence of inhibitory compounds such as hydrogen sulfide (H2S) and methanol (CH3OH) on the catalytic productivity and properties of the polymers in the polymerization process with the Ziegler–Natta catalyst. The investigation involved experimental measurements, computational calculations using DFT, and analysis of various parameters, such as molecular weight, melt flow index, xylene solubility, and reactivity descriptors. The results revealed a clear correlation between the concentration of H2S and methanol and the parameters evaluated. Increasing the H2S concentrations, on average by 0.5 and 1.0 ppm, resulted in a drastic decrease in the polymer’s molecular weight. A directly proportional relationship was observed between the flow rate and the H2S concentration. In the case of methanol, the change occurred from 60 ppm, causing a sharp decrease in the molecular weight of the polymer, which translates into an increase in the fluidity index and a decrease in solubility in xylene. The presence of these inhibitors also affected the catalytic activity, causing a reduction in the productivity of the Ziegler–Natta catalyst. Computational calculations provided a deeper understanding of the molecular behavior and reactivity of the studied compounds. The computational calculations yielded significantly lower results compared to other studies, with values of −69.0 and −43.9 kcal/mol for the Ti-CH3OH and H2S interactions, respectively. These results indicate remarkable stability in the studied interactions and suggest that both adsorptions are highly favorable. |
| publishDate |
2023 |
| dc.date.issued.none.fl_str_mv |
2023-10-12 |
| dc.date.accessioned.none.fl_str_mv |
2024-11-12T13:29:36Z |
| dc.date.available.none.fl_str_mv |
2024-11-12T13:29:36Z |
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Artículo de revista |
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Hernández-Fernández, J.; González-Cuello, R.; Ortega-Toro, R. Evaluation of the Reactivity of Methanol and Hydrogen Sulfide Residues with the Ziegler–Natta Catalyst during Polypropylene Synthesis and Its Effects on Polymer Properties. Polymers 2023, 15, 4061. https://doi.org/10.3390/polym15204061 |
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2073-4360 |
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https://hdl.handle.net/11323/13674 |
| dc.identifier.doi.none.fl_str_mv |
10.3390/polym15204061 |
| dc.identifier.instname.none.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.none.fl_str_mv |
REDICUC - Repositorio CUC |
| dc.identifier.repourl.none.fl_str_mv |
https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Hernández-Fernández, J.; González-Cuello, R.; Ortega-Toro, R. Evaluation of the Reactivity of Methanol and Hydrogen Sulfide Residues with the Ziegler–Natta Catalyst during Polypropylene Synthesis and Its Effects on Polymer Properties. Polymers 2023, 15, 4061. https://doi.org/10.3390/polym15204061 2073-4360 10.3390/polym15204061 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
| url |
https://hdl.handle.net/11323/13674 https://repositorio.cuc.edu.co/ |
| dc.language.iso.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.ispartofjournal.none.fl_str_mv |
Polymers |
| dc.relation.references.none.fl_str_mv |
Guo, X.; Cui, L.; Wang, Y.; Yi, J.; Sun, J.; Liu, Z.; Liu, B. Mechanistic Study on Effect of Electron Donors in Propylene Polymerization Using the Ziegler–Natta Catalyst. J. Phys. Chem. C 2021, 125, 8533–8542. [CrossRef] Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Das Mülheimer Normaldruck-Polyäthylen-Verfahren. Angew. Chem. 1955, 67, 541–547. [CrossRef] Natta, G.; Pino, P.; Corradini, P.; Danusso, F.; Mantica, E.; Mazzanti, G.; Moraglio, G. Crystalline high polymers of α-olefins. J. Am. Chem. Soc. 1955, 77, 1708–1710. [CrossRef] Bahri-Laleh, N.; Hanifpour, A.; Mirmohammadi, S.A.; Poater, A.; Nekoomanesh-Haghighi, M.; Talarico, G.; Cavallo, L. Computational modeling of heterogeneous Ziegler-Natta catalysts for olefins polymerization. Prog. Polym. Sci. 2018, 84, 89–114. [CrossRef] Kumawat, J.K.; Gupta, V.K. Fundamental aspects of heterogeneous Ziegler–Natta olefin polymerization catalysis: An experimental and computational overview. Polym. Chem. 2020, 11, 6107–6128. [CrossRef] Morini, G.; Albizzati, E.; Balbontin, G.; Mingozzi, I.; Sacchi, M.C.; Forlini, F.; Tritto, I. Microstructure Distribution of Polypropylenes Obtained in the Presence of Traditional Phthalate/Silane and Novel Diether Donors: A Tool for Understanding the Role of Electron Donors in MgCl2 -Supported Ziegler−Natta Catalysts. Macromolecules 1996, 29, 5770–5776. [CrossRef] Chadwick, J.C.; Van Kessel, G.M.M.; Sudmeijer, O. Regio- and stereospecificity in propene polymerization with MgCl2-supported Ziegler-Natta catalysts: Effects of hydrogen and the external donor. Macromol. Chem. Phys. 1995, 196, 1431–1437. [CrossRef] Busico, V.; Corradini, P.; De Martino, L.; Proto, A.; Savino, V.; Albizzati, E. Polymerization of propene in the presence of MgCl2 -supported Ziegler-Natta catalysts, 1. The role of ethyl benzoate as ‘internal’ and ‘external’ base. Die Makromol. Chem. 1985, 186, 1279–1288. [CrossRef] Hernández-Fernández, J.; Guerra, Y.; Puello-Polo, E.; Marquez, E. Effects of Different Concentrations of Arsine on the Synthesis and Final Properties of Polypropylene. Polymers 2022, 14, 3123. [CrossRef] [PubMed] Hernández-Fernández, J.; Ortega-Toro, R.; Castro-Suarez, J.R. Theoretical–Experimental Study of the Action of Trace Amounts of Formaldehyde, Propionaldehyde, and Butyraldehyde as Inhibitors of the Ziegler–Natta Catalyst and the Synthesis of an Ethylene–Propylene Copolymer. Polymers 2023, 15, 1098. [CrossRef] [PubMed] Hernández-Fernández, J.; Cano, H.; Aldas, M. Impact of Traces of Hydrogen Sulfide on the Efficiency of Ziegler–Natta Catalyst on the Final Properties of Polypropylene. Polymers 2022, 14, 3910. [CrossRef] Fernández, J.H.; Guerra, Y.; Cano, H. Detection of Bisphenol A and Four Analogues in Atmospheric Emissions in Petrochemical Complexes Producing Polypropylene in South America. Molecules 2022, 27, 4832. [CrossRef] Joaquin, H.-F.; Juan, L.-M. Autocatalytic influence of different levels of arsine on the thermal stability and pyrolysis of polypropylene. J. Anal. Appl. Pyrolysis 2022, 161, 105385. [CrossRef] Hernández-Fernández, J.; Castro-Suarez, J.R.; Toloza, C.A.T. Iron Oxide Powder as Responsible for the Generation of Industrial Polypropylene Waste and as a Co-Catalyst for the Pyrolysis of Non-Additive Resins. Int. J. Mol. Sci. 2022, 23, 11708. [CrossRef] Química Orgánica-Robert Thornton Morrison, Robert Neilson Boyd-Google Libros. Available online: https://books.google.es/ books?hl=es&lr=&id=3b2Yk_dzH70C&oi=fnd&pg=PA1&dq=que+es+la+estereoselectividad&ots=RuxjVqN1Vr&sig=FiWd1HjBzH3wik8w201XexiToc#v=onepage&q&f=false (accessed on 20 July 2023). Chaudhary, V.; Sharma, S. Suspension polymerization technique: Parameters affecting polymer properties and application in oxidation reactions. J. Polym. Res. 2019, 26, 102. [CrossRef] Tangjituabun, K.; Kim, S.Y.; Hiraoka, Y.; Taniike, T.; Terano, M.; Jongsomjit, B.; Praserthdam, P. Poisoning of active sites on ziegler-natta catalyst for propylene polymerization. Chin. J. Polym. Sci. 2008, 26, 547–552. [CrossRef] Hernández-Fernández, J. Quantification of oxygenates, sulphides, thiols and permanent gases in propylene. A multiple linear regression model to predict the loss of efficiency in polypropylene production on an industrial scale. J. Chromatogr. A 2020, 1628, 461478. [CrossRef] [PubMed] Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A.T. Experimental Study of the Impact of Trace Amounts of Acetylene and Methylacetylene on the Synthesis, Mechanical and Thermal Properties of Polypropylene. Int. J. Mol. Sci. 2022, 23, 12148. [CrossRef] Hernández-Fernández, J.; López-Martínez, J. Experimental study of the auto-catalytic effect of triethylaluminum and TiCl4 residuals at the onset of non-additive polypropylene degradation and their impact on thermo-oxidative degradation and pyrolysis. J. Anal. Appl. Pyrolysis 2021, 155, 105052. [CrossRef] Joaquin, H.-F.; Juan, L. Quantification of poisons for Ziegler Natta catalysts and effects on the production of polypropylene by gas chromatographic with simultaneous detection: Pulsed discharge helium ionization, mass spectrometry and flame ionization. J. Chromatogr. A 2020, 1614, 460736. [CrossRef] [PubMed] Hernández-Fernandez, J.; Rodríguez, E. Determination of phenolic antioxidants additives in industrial wastewater from polypropylene production using solid phase extraction with high-performance liquid chromatography. J. Chromatogr. A 2019, 1607, 460442. [CrossRef] [PubMed] Hernández-Fernández, J.; Marulanda, K.; Puello-Polo, E. A new Valorization Route of Petrochemical Wastewater: Recovery of Phenolic Derivatives and their Subsequent Application in a PP Matrix for the Improvement of their Durability in Multiple Applications. J. Polym. Environ. 2023, 31, 2902–2911. [CrossRef] Boyron, O.; Cancelas, A.J.; Taam, M.; Boisson, C.; McKenna, T. A new straightforward method for measuring xylene soluble for high impact polypropylene. Can. J. Chem. Eng. 2017, 95, 939–943. [CrossRef] El Sayed, H.; El Nemr, A.; Esawy, S.A.; Ragab, S. Corrosion inhibitors: Part II: Quantum chemical studies on the corrosion inhibitions of steel in acidic medium by some triazole, oxadiazole and thiadiazole derivatives. Electrochim. Acta 2006, 51, 3957. Gece, G.; Bilgiç, S. Quantum chemical study of some cyclic nitrogen compounds as corrosion inhibitors of steel in NaCl media. Corros. Sci. 2009, 51, 1876. [CrossRef] Piovano, A.; Signorile, M.; Braglia, L.; Torelli, P.; Martini, A.; Wada, T.; Takasao, G.; Taniike, T.; Groppo, E. Electronic Properties of Ti Sites in Ziegler–Natta Catalysts. ACS Catal. 2021, 11, 9949–9961. [CrossRef] Obot, I.B.; Obi-Egbedi, N.O.; Umoren, S.A. Adsorption Characteristics and Corrosion Inhibitive Properties of Clotrimazole for Aluminium Corrosion in Hydrochloric Acid. Int. J. Electrochem. Sci. 2009, 4, 863–877. [CrossRef] Obi-Egbedi, N.O.; Obot, I.B.; El-Khaiary, M.I.; Umoren, S.A.; Ebenso, E.E. Computational simulation and statistical analysis on the relationship between corrosion inhibition efficiency and molecular structure of some phenanthroline derivatives on mild steel surface. Int. J. Electro. Chem. Sci. 2011, 6, 5649. [CrossRef] Hasanov, R.; Sadıko ˘glu, M.; Bilgiç, S. Electrochemical and quantum chemical studies of some Schiff bases on the corrosion of steel in H2SO4 solution. Appl. Surf. Sci. 2007, 253, 3913. [CrossRef] Geerlings, P.; De Proft, F. Chemical reactivity as described by quantum chemical methods. Int. J. Mol. Sci. 2002, 3, 276. [CrossRef] Sahin, M.; Gece, G.; Karcı, F.; Bilgiç, S.J.J.A.E. Experimental and theoretical study of the effect of some heterocyclic compounds on the corrosion of low carbon steel in 3.5% NaCl medium. J. Appl. Electrochem. 2008, 38, 809. [CrossRef] Breket, G.; Hur, E.; Ogretir, C. Quantum chemical studies on some imidazole derivatives as corrosion inhibitors for iron in acidic medium. J. Mol. Struct. (THEOCHEM) 2002, 578, 79–88. [CrossRef] Gómez, B.; Likhanova, N.V.; Domínguez-Aguilar, M.A.; Martínez-Palou, R.; Vela, A.; Gázquez, J.L. Quantum chemical study of the inhibitive properties of 2-pyridyl-azoles. J. Phys. Chem. B 2006, 110, 8928. [CrossRef] [PubMed] Parr, R.G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford University Press: New York, NY, USA, 1989. Bahri-Laleh, N. Interaction of different poisons with MgCl2/TiCl4 based Ziegler-Natta catalysts. Appl. Surf. Sci. 2016, 379, 395–401. [CrossRef] Yan, W.-C.; Dong, T.; Zhou, Y.-N.; Luo, Z.-H. Computational modeling toward full chain of polypropylene production: From molecular to industrial scale. Chem. Eng. Sci. 2023, 269, 118448. [CrossRef] Kawamura-Kuribayashi, H.; Koga, N.; Morokuma, K. An ab initio MO study on ethylene and propylene insertion into the titanium-methyl bond in CH3TiCl2+ as a model of homogeneous olefin polymerization. J. Am. Chem. Soc. 1992, 114, 2359–2366. [CrossRef] |
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© 2023 by the authors. |
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Atribución 4.0 Internacional (CC BY 4.0) |
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Atribución 4.0 Internacional (CC BY 4.0) © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/ http://purl.org/coar/access_right/c_abf2 |
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22 páginas |
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Multidisciplinary Digital Publishing Institute (MDPI) |
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Switzerland |
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Multidisciplinary Digital Publishing Institute (MDPI) |
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Atribución 4.0 Internacional (CC BY 4.0)© 2023 by the authors.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Hernández Fernández, JoaquínGonzález Cuello, RafaelOrtega Toro, Rodrigo2024-11-12T13:29:36Z2024-11-12T13:29:36Z2023-10-12Hernández-Fernández, J.; González-Cuello, R.; Ortega-Toro, R. Evaluation of the Reactivity of Methanol and Hydrogen Sulfide Residues with the Ziegler–Natta Catalyst during Polypropylene Synthesis and Its Effects on Polymer Properties. Polymers 2023, 15, 4061. https://doi.org/10.3390/polym152040612073-4360https://hdl.handle.net/11323/1367410.3390/polym15204061Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/The study focused on the evaluation of the influence of inhibitory compounds such as hydrogen sulfide (H2S) and methanol (CH3OH) on the catalytic productivity and properties of the polymers in the polymerization process with the Ziegler–Natta catalyst. The investigation involved experimental measurements, computational calculations using DFT, and analysis of various parameters, such as molecular weight, melt flow index, xylene solubility, and reactivity descriptors. The results revealed a clear correlation between the concentration of H2S and methanol and the parameters evaluated. Increasing the H2S concentrations, on average by 0.5 and 1.0 ppm, resulted in a drastic decrease in the polymer’s molecular weight. A directly proportional relationship was observed between the flow rate and the H2S concentration. In the case of methanol, the change occurred from 60 ppm, causing a sharp decrease in the molecular weight of the polymer, which translates into an increase in the fluidity index and a decrease in solubility in xylene. The presence of these inhibitors also affected the catalytic activity, causing a reduction in the productivity of the Ziegler–Natta catalyst. Computational calculations provided a deeper understanding of the molecular behavior and reactivity of the studied compounds. The computational calculations yielded significantly lower results compared to other studies, with values of −69.0 and −43.9 kcal/mol for the Ti-CH3OH and H2S interactions, respectively. These results indicate remarkable stability in the studied interactions and suggest that both adsorptions are highly favorable.22 páginasapplication/pdfengMultidisciplinary Digital Publishing Institute (MDPI)Switzerlandhttps://www.mdpi.com/2073-4360/15/20/4061Evaluation of the reactivity of methanol and hydrogen sulfide residues with the Ziegler–Natta catalyst during polypropylene synthesis and Its effects on polymer propertiesArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85PolymersGuo, X.; Cui, L.; Wang, Y.; Yi, J.; Sun, J.; Liu, Z.; Liu, B. Mechanistic Study on Effect of Electron Donors in Propylene Polymerization Using the Ziegler–Natta Catalyst. J. Phys. Chem. C 2021, 125, 8533–8542. [CrossRef]Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Das Mülheimer Normaldruck-Polyäthylen-Verfahren. Angew. Chem. 1955, 67, 541–547. [CrossRef]Natta, G.; Pino, P.; Corradini, P.; Danusso, F.; Mantica, E.; Mazzanti, G.; Moraglio, G. Crystalline high polymers of α-olefins. J. Am. Chem. Soc. 1955, 77, 1708–1710. [CrossRef]Bahri-Laleh, N.; Hanifpour, A.; Mirmohammadi, S.A.; Poater, A.; Nekoomanesh-Haghighi, M.; Talarico, G.; Cavallo, L. Computational modeling of heterogeneous Ziegler-Natta catalysts for olefins polymerization. Prog. Polym. Sci. 2018, 84, 89–114. [CrossRef]Kumawat, J.K.; Gupta, V.K. Fundamental aspects of heterogeneous Ziegler–Natta olefin polymerization catalysis: An experimental and computational overview. Polym. Chem. 2020, 11, 6107–6128. [CrossRef]Morini, G.; Albizzati, E.; Balbontin, G.; Mingozzi, I.; Sacchi, M.C.; Forlini, F.; Tritto, I. Microstructure Distribution of Polypropylenes Obtained in the Presence of Traditional Phthalate/Silane and Novel Diether Donors: A Tool for Understanding the Role of Electron Donors in MgCl2 -Supported Ziegler−Natta Catalysts. Macromolecules 1996, 29, 5770–5776. [CrossRef]Chadwick, J.C.; Van Kessel, G.M.M.; Sudmeijer, O. Regio- and stereospecificity in propene polymerization with MgCl2-supported Ziegler-Natta catalysts: Effects of hydrogen and the external donor. Macromol. Chem. Phys. 1995, 196, 1431–1437. [CrossRef]Busico, V.; Corradini, P.; De Martino, L.; Proto, A.; Savino, V.; Albizzati, E. Polymerization of propene in the presence of MgCl2 -supported Ziegler-Natta catalysts, 1. The role of ethyl benzoate as ‘internal’ and ‘external’ base. Die Makromol. Chem. 1985, 186, 1279–1288. [CrossRef]Hernández-Fernández, J.; Guerra, Y.; Puello-Polo, E.; Marquez, E. Effects of Different Concentrations of Arsine on the Synthesis and Final Properties of Polypropylene. Polymers 2022, 14, 3123. [CrossRef] [PubMed]Hernández-Fernández, J.; Ortega-Toro, R.; Castro-Suarez, J.R. Theoretical–Experimental Study of the Action of Trace Amounts of Formaldehyde, Propionaldehyde, and Butyraldehyde as Inhibitors of the Ziegler–Natta Catalyst and the Synthesis of an Ethylene–Propylene Copolymer. Polymers 2023, 15, 1098. [CrossRef] [PubMed]Hernández-Fernández, J.; Cano, H.; Aldas, M. Impact of Traces of Hydrogen Sulfide on the Efficiency of Ziegler–Natta Catalyst on the Final Properties of Polypropylene. Polymers 2022, 14, 3910. [CrossRef]Fernández, J.H.; Guerra, Y.; Cano, H. Detection of Bisphenol A and Four Analogues in Atmospheric Emissions in Petrochemical Complexes Producing Polypropylene in South America. Molecules 2022, 27, 4832. [CrossRef]Joaquin, H.-F.; Juan, L.-M. Autocatalytic influence of different levels of arsine on the thermal stability and pyrolysis of polypropylene. J. Anal. Appl. Pyrolysis 2022, 161, 105385. [CrossRef]Hernández-Fernández, J.; Castro-Suarez, J.R.; Toloza, C.A.T. Iron Oxide Powder as Responsible for the Generation of Industrial Polypropylene Waste and as a Co-Catalyst for the Pyrolysis of Non-Additive Resins. Int. J. Mol. Sci. 2022, 23, 11708. [CrossRef]Química Orgánica-Robert Thornton Morrison, Robert Neilson Boyd-Google Libros. Available online: https://books.google.es/ books?hl=es&lr=&id=3b2Yk_dzH70C&oi=fnd&pg=PA1&dq=que+es+la+estereoselectividad&ots=RuxjVqN1Vr&sig=FiWd1HjBzH3wik8w201XexiToc#v=onepage&q&f=false (accessed on 20 July 2023).Chaudhary, V.; Sharma, S. Suspension polymerization technique: Parameters affecting polymer properties and application in oxidation reactions. J. Polym. Res. 2019, 26, 102. [CrossRef]Tangjituabun, K.; Kim, S.Y.; Hiraoka, Y.; Taniike, T.; Terano, M.; Jongsomjit, B.; Praserthdam, P. Poisoning of active sites on ziegler-natta catalyst for propylene polymerization. Chin. J. Polym. Sci. 2008, 26, 547–552. [CrossRef]Hernández-Fernández, J. 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[CrossRef]2212015Ziegler–Natta polymerizationHydrogen sulfideMethanolCatalyst productivityMolecular weightMelt flow indexXylene solubilityDFT calculationsReactivity descriptorsPublicationORIGINALEvaluation of the Reactivity of Methanol and Hydrogen Sulfide.pdfEvaluation of the Reactivity of Methanol and Hydrogen Sulfide.pdfapplication/pdf6326291https://repositorio.cuc.edu.co/bitstreams/5ae02d8b-13f2-46cc-b598-ec5471df234c/downloadc784e92c06bf398f46c8958343b5f496MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-815543https://repositorio.cuc.edu.co/bitstreams/8fc104e6-e0c7-487c-8342-b7f98cd62b35/download73a5432e0b76442b22b026844140d683MD52TEXTEvaluation of the Reactivity of Methanol and Hydrogen Sulfide.pdf.txtEvaluation of the Reactivity of Methanol and Hydrogen Sulfide.pdf.txtExtracted texttext/plain100660https://repositorio.cuc.edu.co/bitstreams/2e5b0c25-6829-47d5-a5fa-6ea512fe7858/download5e3d4238b072782257a76bd63947cf52MD53THUMBNAILEvaluation of the Reactivity of Methanol and Hydrogen Sulfide.pdf.jpgEvaluation of the Reactivity of Methanol and Hydrogen Sulfide.pdf.jpgGenerated Thumbnailimage/jpeg16697https://repositorio.cuc.edu.co/bitstreams/84f4b5ff-ffd1-49a6-9393-c66084f8120b/download28ace89619d552d61d178dbc53064c3eMD5411323/13674oai:repositorio.cuc.edu.co:11323/136742024-11-13 03:00:46.578https://creativecommons.org/licenses/by/4.0/© 2023 by the authors.open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa 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ara ejercer estos derechos sobre la Obra tal y como se indica a continuación:</p>
    <ol type="a">
      <li>Reproducir la Obra, incorporar la Obra en una o más Obras Colectivas, y reproducir la Obra incorporada en las Obras Colectivas.</li>
      <li>Distribuir copias o fonogramas de las Obras, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública, incluyéndolas como incorporadas en Obras Colectivas, según corresponda.</li>
      <li>Distribuir copias de las Obras Derivadas que se generen, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública.</li>
    </ol>
    <p>Los derechos mencionados anteriormente pueden ser ejercidos en todos los medios y formatos, actualmente conocidos o que se inventen en el futuro. Los derechos antes mencionados incluyen el derecho a realizar dichas modificaciones en la medida que sean técnicamente necesarias para ejercer los derechos en otro medio o formatos, pero de otra manera usted no está autorizado para realizar obras derivadas. Todos los derechos no otorgados expresamente por el Licenciante quedan por este medio reservados, incluyendo pero sin limitarse a aquellos que se mencionan en las secciones 4(d) y 4(e).</p>
  </li>
  <br/>
  <li>
    Restricciones.
    <p>La licencia otorgada en la anterior Sección 3 está expresamente sujeta y limitada por las siguientes restricciones:</p>
    <ol type="a">
      <li>Usted puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra sólo bajo las condiciones de esta Licencia, y Usted debe incluir una copia de esta licencia o del Identificador Universal de Recursos de la misma con cada copia de la Obra que distribuya, exhiba públicamente, ejecute públicamente o ponga a disposición pública. No es posible ofrecer o imponer ninguna condición sobre la Obra que altere o limite las condiciones de esta Licencia o el ejercicio de los derechos de los destinatarios otorgados en este documento. No es posible sublicenciar la Obra. Usted debe mantener intactos todos los avisos que hagan referencia a esta Licencia y a la cláusula de limitación de garantías. Usted no puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra con alguna medida tecnológica que controle el acceso o la utilización de ella de una forma que sea inconsistente con las condiciones de esta Licencia. Lo anterior se aplica a la Obra incorporada a una Obra Colectiva, pero esto no exige que la Obra Colectiva aparte de la obra misma quede sujeta a las condiciones de esta Licencia. Si Usted crea una Obra Colectiva, previo aviso de cualquier Licenciante debe, en la medida de lo posible, eliminar de la Obra Colectiva cualquier referencia a dicho Licenciante o al Autor Original, según lo solicitado por el Licenciante y conforme lo exige la cláusula 4(c).</li>
      <li>Usted no puede ejercer ninguno de los derechos que le han sido otorgados en la Sección 3 precedente de modo que estén principalmente destinados o directamente dirigidos a conseguir un provecho comercial o una compensación monetaria privada. El intercambio de la Obra por otras obras protegidas por derechos de autor, ya sea a través de un sistema para compartir archivos digitales (digital file-sharing) o de cualquier otra manera no será considerado como estar destinado principalmente o dirigido directamente a conseguir un provecho comercial o una compensación monetaria privada, siempre que no se realice un pago mediante una compensación monetaria en relación con el intercambio de obras protegidas por el derecho de autor.</li>
      <li>Si usted distribuye, exhibe públicamente, ejecuta públicamente o ejecuta públicamente en forma digital la Obra o cualquier Obra Derivada u Obra Colectiva, Usted debe mantener intacta toda la información de derecho de autor de la Obra y proporcionar, de forma razonable según el medio o manera que Usted esté utilizando: (i) el nombre del Autor Original si está provisto (o seudónimo, si fuere aplicable), y/o (ii) el nombre de la parte o las partes que el Autor Original y/o el Licenciante hubieren designado para la atribución (v.g., un instituto patrocinador, editorial, publicación) en la información de los derechos de autor del Licenciante, términos de servicios o de otras formas razonables; el título de la Obra si está provisto; en la medida de lo razonablemente factible y, si está provisto, el Identificador Uniforme de Recursos (Uniform Resource Identifier) que el Licenciante especifica para ser asociado con la Obra, salvo que tal URI no se refiera a la nota sobre los derechos de autor o a la información sobre el licenciamiento de la Obra; y en el caso de una Obra Derivada, atribuir el crédito identificando el uso de la Obra en la Obra Derivada (v.g., "Traducción Francesa de la Obra del Autor Original," o "Guión Cinematográfico basado en la Obra original del Autor Original"). Tal crédito puede ser implementado de cualquier forma razonable; en el caso, sin embargo, de Obras Derivadas u Obras Colectivas, tal crédito aparecerá, como mínimo, donde aparece el crédito de cualquier otro autor comparable y de una manera, al menos, tan destacada como el crédito de otro autor comparable.</li>
      <li>
        Para evitar toda confusión, el Licenciante aclara que, cuando la obra es una composición musical:
        <ol type="i">
          <li>Regalías por interpretación y ejecución bajo licencias generales. El Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública o la ejecución pública digital de la obra y de recolectar, sea individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, SAYCO), las regalías por la ejecución pública o por la ejecución pública digital de la obra (por ejemplo Webcast) licenciada bajo licencias generales, si la interpretación o ejecución de la obra está primordialmente orientada por o dirigida a la obtención de una ventaja comercial o una compensación monetaria privada.</li>
          <li>Regalías por Fonogramas. El Licenciante se reserva el derecho exclusivo de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, los consagrados por la SAYCO), una agencia de derechos musicales o algún agente designado, las regalías por cualquier fonograma que Usted cree a partir de la obra (“versión cover”) y distribuya, en los términos del régimen de derechos de autor, si la creación o distribución de esa versión cover está primordialmente destinada o dirigida a obtener una ventaja comercial o una compensación monetaria privada.</li>
        </ol>
      </li>
      <li>Gestión de Derechos de Autor sobre Interpretaciones y Ejecuciones Digitales (WebCasting). Para evitar toda confusión, el Licenciante aclara que, cuando la obra sea un fonograma, el Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública digital de la obra (por ejemplo, webcast) y de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, ACINPRO), las regalías por la ejecución pública digital de la obra (por ejemplo, webcast), sujeta a las disposiciones aplicables del régimen de Derecho de Autor, si esta ejecución pública digital está primordialmente dirigida a obtener una ventaja comercial o una compensación monetaria privada.</li>
    </ol>
  </li>
  <br/>
  <li>
    Representaciones, Garantías y Limitaciones de Responsabilidad.
    <p>A MENOS QUE LAS PARTES LO ACORDARAN DE OTRA FORMA POR ESCRITO, EL LICENCIANTE OFRECE LA OBRA (EN EL ESTADO EN EL QUE SE ENCUENTRA) “TAL CUAL”, SIN BRINDAR GARANTÍAS DE CLASE ALGUNA RESPECTO DE LA OBRA, YA SEA EXPRESA, IMPLÍCITA, LEGAL O CUALQUIERA OTRA, INCLUYENDO, SIN LIMITARSE A ELLAS, GARANTÍAS DE TITULARIDAD, COMERCIABILIDAD, ADAPTABILIDAD O ADECUACIÓN A PROPÓSITO DETERMINADO, AUSENCIA DE INFRACCIÓN, DE AUSENCIA DE DEFECTOS LATENTES O DE OTRO TIPO, O LA PRESENCIA O AUSENCIA DE ERRORES, SEAN O NO DESCUBRIBLES (PUEDAN O NO SER ESTOS DESCUBIERTOS). ALGUNAS JURISDICCIONES NO PERMITEN LA EXCLUSIÓN DE GARANTÍAS IMPLÍCITAS, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.</p>
  </li>
  <br/>
  <li>
    Limitación de responsabilidad.
    <p>A MENOS QUE LO EXIJA EXPRESAMENTE LA LEY APLICABLE, EL LICENCIANTE NO SERÁ RESPONSABLE ANTE USTED POR DAÑO ALGUNO, SEA POR RESPONSABILIDAD EXTRACONTRACTUAL, PRECONTRACTUAL O CONTRACTUAL, OBJETIVA O SUBJETIVA, SE TRATE DE DAÑOS MORALES O PATRIMONIALES, DIRECTOS O INDIRECTOS, PREVISTOS O IMPREVISTOS PRODUCIDOS POR EL USO DE ESTA LICENCIA O DE LA OBRA, AUN CUANDO EL LICENCIANTE HAYA SIDO ADVERTIDO DE LA POSIBILIDAD DE DICHOS DAÑOS. ALGUNAS LEYES NO PERMITEN LA EXCLUSIÓN DE CIERTA RESPONSABILIDAD, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.</p>
  </li>
  <br/>
  <li>
    Término.
    <ol type="a">
      <li>Esta Licencia y los derechos otorgados en virtud de ella terminarán automáticamente si Usted infringe alguna condición establecida en ella. Sin embargo, los individuos o entidades que han recibido Obras Derivadas o Colectivas de Usted de conformidad con esta Licencia, no verán terminadas sus licencias, siempre que estos individuos o entidades sigan cumpliendo íntegramente las condiciones de estas licencias. Las Secciones 1, 2, 5, 6, 7, y 8 subsistirán a cualquier terminación de esta Licencia.</li>
      <li>Sujeta a las condiciones y términos anteriores, la licencia otorgada aquí es perpetua (durante el período de vigencia de los derechos de autor de la obra). No obstante lo anterior, el Licenciante se reserva el derecho a publicar y/o estrenar la Obra bajo condiciones de licencia diferentes o a dejar de distribuirla en los términos de esta Licencia en cualquier momento; en el entendido, sin embargo, que esa elección no servirá para revocar esta licencia o que deba ser otorgada , bajo los términos de esta licencia), y esta licencia continuará en pleno vigor y efecto a menos que sea terminada como se expresa atrás. La Licencia revocada continuará siendo plenamente vigente y efectiva si no se le da término en las condiciones indicadas anteriormente.</li>
    </ol>
  </li>
  <br/>
  <li>
    Varios.
    <ol type="a">
      <li>Cada vez que Usted distribuya o ponga a disposición pública la Obra o una Obra Colectiva, el Licenciante ofrecerá al destinatario una licencia en los mismos términos y condiciones que la licencia otorgada a Usted bajo esta Licencia.</li>
      <li>Si alguna disposición de esta Licencia resulta invalidada o no exigible, según la legislación vigente, esto no afectará ni la validez ni la aplicabilidad del resto de condiciones de esta Licencia y, sin acción adicional por parte de los sujetos de este acuerdo, aquélla se entenderá reformada lo mínimo necesario para hacer que dicha disposición sea válida y exigible.</li>
      <li>Ningún término o disposición de esta Licencia se estimará renunciada y ninguna violación de ella será consentida a menos que esa renuncia o consentimiento sea otorgado por escrito y firmado por la parte que renuncie o consienta.</li>
      <li>Esta Licencia refleja el acuerdo pleno entre las partes respecto a la Obra aquí licenciada. No hay arreglos, acuerdos o declaraciones respecto a la Obra que no estén especificados en este documento. El Licenciante no se verá limitado por ninguna disposición adicional que pueda surgir en alguna comunicación emanada de Usted. Esta Licencia no puede ser modificada sin el consentimiento mutuo por escrito del Licenciante y Usted.</li>
    </ol>
  </li>
  <br/>
</ol>
 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