Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis

In this experimental–theoretical study, the effect of furan on Ziegler–Natta catalyst productivity, melt flow index (MFI), and mechanical properties of polypropylene were investigated. Through the analysis of the global and local reactivity of the reagents, it was determined that the furan acts as a...

Full description

Autores:
Hernández-Fernández, Joaquín
Puello-Polo, Esneyder
Marquez, Edgar
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:11323/13485
Acceso en línea:
https://hdl.handle.net/11323/13485
https://repositorio.cuc.edu.co/
Palabra clave:
Furan
Ziegler–Natta catalyst
Polypropylene synthesis
Flow rate
Density functional theory (DFT)
Mechanical properties
Adsorption affinity
Rights
openAccess
License
Atribución 4.0 Internacional (CC BY 4.0)
id RCUC2_032bce6939faa198dcb971706e3411f1
oai_identifier_str oai:repositorio.cuc.edu.co:11323/13485
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.eng.fl_str_mv Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
title Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
spellingShingle Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
Furan
Ziegler–Natta catalyst
Polypropylene synthesis
Flow rate
Density functional theory (DFT)
Mechanical properties
Adsorption affinity
title_short Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
title_full Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
title_fullStr Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
title_full_unstemmed Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
title_sort Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesis
dc.creator.fl_str_mv Hernández-Fernández, Joaquín
Puello-Polo, Esneyder
Marquez, Edgar
dc.contributor.author.none.fl_str_mv Hernández-Fernández, Joaquín
Puello-Polo, Esneyder
Marquez, Edgar
dc.subject.proposal.eng.fl_str_mv Furan
Ziegler–Natta catalyst
Polypropylene synthesis
Flow rate
Density functional theory (DFT)
Mechanical properties
Adsorption affinity
topic Furan
Ziegler–Natta catalyst
Polypropylene synthesis
Flow rate
Density functional theory (DFT)
Mechanical properties
Adsorption affinity
description In this experimental–theoretical study, the effect of furan on Ziegler–Natta catalyst productivity, melt flow index (MFI), and mechanical properties of polypropylene were investigated. Through the analysis of the global and local reactivity of the reagents, it was determined that the furan acts as an electron donor. In contrast, the titanium of the ZN catalyst acts as an electron acceptor. It is postulated that this difference in reactivity could lead to forming a furan–titanium complex, which blocks the catalyst’s active sites and reduces its efficiency for propylene polymerization. Theoretical results showed a high adsorption affinity of furan to the active site of the Ti catalyst, indicating that furan tends to bind strongly to the catalyst, thus blocking the active sites and decreasing the availability for propylene polymerization. The experimental data revealed that the presence of furan significantly reduced the productivity of the ZN catalyst by 10, 20, and 41% for concentrations of 6, 12.23, and 25.03 ppm furan, respectively. In addition, a proportional relationship was observed between the furan concentration and the MFI melt index of the polymer, where the higher the furan concentration, the higher the MFI. Likewise, the presence of furan negatively affected the mechanical properties of polypropylene, especially the impact Izod value, with percentage decreases of 9, 18, and 22% for concentrations of 6, 12.23, and 25.03 ppm furan, respectively.
publishDate 2023
dc.date.issued.none.fl_str_mv 2023-09-21
dc.date.accessioned.none.fl_str_mv 2024-10-23T12:48:37Z
dc.date.available.none.fl_str_mv 2024-10-23T12:48:37Z
dc.type.none.fl_str_mv Artículo de revista
dc.type.coar.none.fl_str_mv http://purl.org/coar/resource_type/c_2df8fbb1
dc.type.content.none.fl_str_mv Text
dc.type.driver.none.fl_str_mv info:eu-repo/semantics/article
dc.type.redcol.none.fl_str_mv http://purl.org/redcol/resource_type/ART
dc.type.version.none.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.coarversion.none.fl_str_mv http://purl.org/coar/version/c_970fb48d4fbd8a85
format http://purl.org/coar/resource_type/c_2df8fbb1
status_str publishedVersion
dc.identifier.citation.none.fl_str_mv Hernández-Fernández, J.; Puello-Polo, E.; Marquez, E. Experimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis. Int. J. Mol. Sci. 2023, 24, 14368. https://doi.org/ 10.3390/ijms241814368
dc.identifier.issn.none.fl_str_mv 1661-6596
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/13485
dc.identifier.doi.none.fl_str_mv 10.3390/ijms241814368
dc.identifier.eissn.none.fl_str_mv 1422-0067
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.; Puello-Polo, E.; Marquez, E. Experimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis. Int. J. Mol. Sci. 2023, 24, 14368. https://doi.org/ 10.3390/ijms241814368
1661-6596
10.3390/ijms241814368
1422-0067
Corporación Universidad de la Costa
REDICUC - Repositorio CUC
url https://hdl.handle.net/11323/13485
https://repositorio.cuc.edu.co/
dc.language.iso.none.fl_str_mv eng
language eng
dc.relation.ispartofjournal.none.fl_str_mv International journal of molecular sciences
dc.relation.references.none.fl_str_mv 1. Bora, R.R.; Wang, R.; You, F. Waste polypropylene plastic recycling toward climate change mitigation and circular economy: Energy, environmental, and technoeconomic perspectives. ACS Sustain. Chem. Eng. 2020, 8, 16350–16363. [CrossRef]
2. Alsabri, A.; Tahir, F.; Al-Ghamdi, S.G. Environmental impacts of polypropylene (PP) production and prospects of its recycling in the GCC region. Mater. Today Proc. 2021, 56, 2245–2251. [CrossRef]
3. 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]
4. Kibria, G.; Masuk, N.I.; Safayet, R.; Nguyen, H.Q.; Mourshed, M. Plastic Waste: Challenges and Opportunities to Mitigate Pollution and Effective Management. Int. J. Environ. Res. 2023, 17, 20. [CrossRef] [PubMed]
5. Blazsó, M. Recent trends in analytical and applied pyrolysis of polymers. J. Anal. Appl. Pyrolysis 1997, 39, 1–25. [CrossRef]
6. Kruse, T.M.; Wong, H.-W.; Broadbelt, L.J. Mechanistic Modeling of Polymer Pyrolysis: Polypropylene. Macromolecules 2003, 36, 9594–9607. [CrossRef]
7. Crews, C.; Castle, L. A review of the occurrence, formation and analysis of furan in heat-processed foods. Trends Food Sci. Technol. 2007, 18, 365–372. [CrossRef]
8. Vranová, J.; Ciesarová, Z. Furan in Food-a Review. Czech J. Food Sci. 2009, 27, 1–10. [CrossRef]
9. Seok, Y.-J.; Her, J.-Y.; Kim, Y.-G.; Kim, M.Y.; Jeong, S.Y.; Kim, M.K.; Lee, J.-Y.; Kim, C.-I.; Yoon, H.-J.; Lee, K.-G. Furan in Thermally Processed Foods—A Review. Toxicol. Res. 2015, 31, 241–253. [CrossRef]
10. Mogol, B.A.; Gökmen, V. Thermal process contaminants: Acrylamide, chloropropanols and furan. Curr. Opin. Food Sci. 2016, 7, 86–92. [CrossRef]
11. Gandini, A. The application of the Diels-Alder reaction to polymer syntheses based on furan/maleimide reversible couplings. Polímeros 2005, 15, 95–101. [CrossRef]
12. Gandini, A. The behaviour of furan derivatives in polymerization reactions. Adv. Polym. Sci. 1977, 25, 47–96. [CrossRef]
13. Hernández-Fernández, J.; Puello-Polo, E.; Márquez, E. Furan as Impurity in Green Ethylene and Its Effects on the Productivity of Random Ethylene–Propylene Copolymer Synthesis and Its Thermal and Mechanical Properties. Polymers 2023, 15, 2264. [CrossRef]
14. Pavon, C.; Aldas, M.; Hernández-Fernández, J.; López-Martínez, J. Comparative characterization of gum rosins for their use as sustainable additives in polymeric matrices. J. Appl. Polym. Sci. 2021, 139, 51734. [CrossRef]
15. Hernández-Fernández, J.; Guerra, Y.; Espinosa, E. Development and Application of a Principal Component Analysis Model to Quantify the Green Ethylene Content in Virgin Impact Copolymer Resins during Their Synthesis on an Industrial Scale. J. Polym. Environ. 2022, 30, 4800–4808. [CrossRef]
16. Cáceres, C.A.C.; Canevarolo, S.V. Correlação entre o Índice de Fluxo à Fusão e a Função da Distribuição de Cisão de Cadeia durante a degradação termo-mecânica do polipropileno. Polímeros 2006, 16, 294–298. [CrossRef]
17. Ferg, E.; Bolo, L. A correlation between the variable melt flow index and the molecular mass distribution of virgin and recycled polypropylene used in the manufacturing of battery cases. Polym. Test. 2013, 32, 1452–1459. [CrossRef]
18. 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]
19. 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]
20. Lorenzo, M.L.R. Determinación y Evaluación de las Emisiones de Dioxinas y Furanos en la Producción de Cemento en España. 2008. Available online: https://dialnet.unirioja.es/servlet/tesis?codigo=17310&info=resumen&idioma=SPA (accessed on 5 August 2023).
21. Sarra, A.J.; Clave, P. Dioxinas y Furanos Derivados de la Combustión. In Perspectivas; Revista Científica de la Universidad de Belgrano: Buenos Aires, Argentina, 2018; Volume 1. Available online: https://revistas.ub.edu.ar/index.php/Perspectivas/ article/view/15 (accessed on 5 August 2023).
22. 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]
23. Hernandez-Fernandez, J.; Lambis, H.; Reyes, R.V. Application of Pyrolysis for the Evaluation of Organic Compounds in Medical Plastic Waste Generated in the City of Cartagena-Colombia Applying TG-GC/MS. Int. J. Mol. Sci. 2023, 24, 5397. [CrossRef]
24. 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]
25. 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]
26. 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 2019, 1614, 460736. [CrossRef]
27. 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]
28. Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Development and validation of a methodology for quantifying partsper-billion levels of arsine and phosphine in nitrogen, hydrogen and liquefied petroleum gas using a variable pressure sampler coupled to gas chromatography-mass spectrometry. J. Chromatogr. A 2021, 1637, 461833. [CrossRef]
29. Fernández, J.H.; Cano, H.; Guerra, Y.; Polo, E.P.; Ríos-Rojas, J.F.; Vivas-Reyes, R.; Oviedo, J. Identification and Quantification of Microplastics in Effluents of Wastewater Treatment Plant by Differential Scanning Calorimetry (DSC). Sustainability 2022, 14, 4920. [CrossRef]
30. Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Quantification and elimination of substituted synthetic phenols and volatile organic compounds in the wastewater treatment plant during the production of industrial scale polypropylene. Chemosphere 2021, 263, 128027. [CrossRef]
31. Hernández-Fernández, J.; Rayón, E.; López, J.; Arrieta, M.P. Enhancing the Thermal Stability of Polypropylene by Blending with Low Amounts of Natural Antioxidants. Macromol. Mater. Eng. 2019, 304, 1900379. [CrossRef]
32. Pavon, C.; Aldas, M.; López-Martínez, J.; Hernández-Fernández, J.; Arrieta, M.P. Films Based on Thermoplastic Starch Blended with Pine Resin Derivatives for Food Packaging. Foods 2021, 10, 1171. [CrossRef]
33. 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]
34. Gómez-Contreras, P.; Figueroa-Lopez, K.J.; Hernández-Fernández, J.; Rodríguez, M.C.; Ortega-Toro, R. Effect of Different Essential Oils on the Properties of Edible Coatings Based on Yam (Dioscorea rotundata L.) Starch and Its Application in Strawberry (Fragaria vesca L.) Preservation. Appl. Sci. 2021, 11, 11057. [CrossRef]
35. Chacon, H.; Cano, H.; Fernández, J.H.; Guerra, Y.; Puello-Polo, E.; Ríos-Rojas, J.F.; Ruiz, Y. Effect of Addition of Polyurea as an Aggregate in Mortars: Analysis of Microstructure and Strength. Polymers 2022, 14, 1753. [CrossRef]
36. Smith, M.B. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure; John Wiley & Sons: Hoboken, NJ, USA, 2020
37. Gayatri, G.; Sastry, G.N. Bottlenecks in the prediction of regioselectivity of [4 + 2] cycloaddition reactions: An assessment of reactivity descriptors. J. Chem. Sci. 2005, 117, 573–582. [CrossRef]
38. Domingo, L.R.; Picher, M.T.; Sáez, J.A. Toward an understanding of the unexpected regioselective Hetero-Diels-Alder reactions of asymmetric tetrazines with electron-rich ethylenes: A DFT study. J. Org. Chem. 2009, 74, 2726–2735. [CrossRef]
39. Parr, R.G.; Gadre, S.R.; Bartolotti, L.J. Local density functional theory of atoms and molecules. Proc. Natl. Acad. Sci. USA 1979, 76, 2522–2526. [CrossRef]
40. Parr, R.G.; Yang, W. Density Functional Approach to the Frontier-Electron Theory of Chemical Reactivity. J. Am. Chem. Soc. 1984, 106, 4049–4050. [CrossRef]
41. Domingo, L.R.; Aurell, M.; Pérez, P.; Contreras, R. Quantitative characterization of the global electrophilicity power of common diene/dienophile pairs in Diels–Alder reactions. Tetrahedron 2002, 58, 4417–4423. [CrossRef]
42. Berkowitz, M.; Parr, R.G. Molecular hardness and softness, local hardness and softness, hardness and softness kernels, and relations among these quantities. J. Chem. Phys. 1988, 88, 2554–2557. [CrossRef]
43. Langenaeker, W.; de Proft, F.; Geerlings, P. Development of local hardness-related reactivity indices: Their application in a study of the SE at monosubstituted benzenes within the HSAB context. J. Phys. Chem. 1995, 99, 6424–6431. [CrossRef]
44. Chamorro, E.; Chattaraj, P.K.; Fuentealba, P. Variation of the Electrophilicity Index along the Reaction Path. J. Phys. Chem. A 2003, 107, 7068–7072. [CrossRef] [PubMed]
45. Pérez, P.; Domingo, L.R.; Duque-Noreña, M.; Chamorro, E. A condensed-to-atom nucleophilicity index. An application to the director effects on the electrophilic aromatic substitutions. J. Mol. Struct. THEOCHEM 2008, 895, 86–91. [CrossRef]
46. Fuentealba, P.; Pérez, P.; Contreras, R. On the condensed Fukui function. J. Chem. Phys. 2000, 113, 2544–2551. [CrossRef]
47. Neihsial, S.; Lyngdoh, R.D. Novel H-bonded base pairs as potential repeat units for information-bearing macromolecular duplexes: A B3LYP/6-31G∗ search. J. Mol. Struct. THEOCHEM 2007, 806, 213–221. [CrossRef]
48. Shubhra, Q.T.H.; Alam, A.K.M.M.; Quaiyyum, M.A. Mechanical properties of polypropylene composites: A review. J. Thermoplast. Compos. Mater. 2011, 26, 362–391. [CrossRef]
dc.relation.citationendpage.none.fl_str_mv 12
dc.relation.citationstartpage.none.fl_str_mv 1
dc.relation.citationissue.none.fl_str_mv 18
dc.relation.citationvolume.none.fl_str_mv 24
dc.rights.eng.fl_str_mv ©2023 by the authors. Licensee MDPI, Basel, Switzerland.
dc.rights.license.none.fl_str_mv Atribución 4.0 Internacional (CC BY 4.0)
dc.rights.uri.none.fl_str_mv https://creativecommons.org/licenses/by/4.0/
dc.rights.accessrights.none.fl_str_mv info:eu-repo/semantics/openAccess
dc.rights.coar.none.fl_str_mv http://purl.org/coar/access_right/c_abf2
rights_invalid_str_mv Atribución 4.0 Internacional (CC BY 4.0)
©2023 by the authors. Licensee MDPI, Basel, Switzerland.
https://creativecommons.org/licenses/by/4.0/
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.extent.none.fl_str_mv 12 páginas
dc.format.mimetype.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute (MDPI)
dc.publisher.place.none.fl_str_mv Switzerland
publisher.none.fl_str_mv Multidisciplinary Digital Publishing Institute (MDPI)
dc.source.none.fl_str_mv https://www.mdpi.com/1422-0067/24/18/14368
institution Corporación Universidad de la Costa
bitstream.url.fl_str_mv https://repositorio.cuc.edu.co/bitstreams/90bfa7d2-2d42-4f98-8eb6-9cfe2883b489/download
https://repositorio.cuc.edu.co/bitstreams/580bbedd-6387-4191-b81c-a17b771ab61f/download
https://repositorio.cuc.edu.co/bitstreams/78eeca8d-9378-4eaa-8899-81ec17df23ff/download
https://repositorio.cuc.edu.co/bitstreams/1149b342-6941-4d9c-9610-aa870ce5bdfd/download
bitstream.checksum.fl_str_mv e56b38be0992015287d838dfdb72f396
73a5432e0b76442b22b026844140d683
dfae9c09eb67f43dcdd640e660f3d588
3ea5ddffa5674280d25bbb858dd7f2b6
bitstream.checksumAlgorithm.fl_str_mv MD5
MD5
MD5
MD5
repository.name.fl_str_mv Repositorio de la Universidad de la Costa CUC
repository.mail.fl_str_mv repdigital@cuc.edu.co
_version_ 1828166894196097024
spelling Atribución 4.0 Internacional (CC BY 4.0)©2023 by the authors. Licensee MDPI, Basel, Switzerland.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Hernández-Fernández, JoaquínPuello-Polo, EsneyderMarquez, Edgar2024-10-23T12:48:37Z2024-10-23T12:48:37Z2023-09-21Hernández-Fernández, J.; Puello-Polo, E.; Marquez, E. Experimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis. Int. J. Mol. Sci. 2023, 24, 14368. https://doi.org/ 10.3390/ijms2418143681661-6596https://hdl.handle.net/11323/1348510.3390/ijms2418143681422-0067Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/In this experimental–theoretical study, the effect of furan on Ziegler–Natta catalyst productivity, melt flow index (MFI), and mechanical properties of polypropylene were investigated. Through the analysis of the global and local reactivity of the reagents, it was determined that the furan acts as an electron donor. In contrast, the titanium of the ZN catalyst acts as an electron acceptor. It is postulated that this difference in reactivity could lead to forming a furan–titanium complex, which blocks the catalyst’s active sites and reduces its efficiency for propylene polymerization. Theoretical results showed a high adsorption affinity of furan to the active site of the Ti catalyst, indicating that furan tends to bind strongly to the catalyst, thus blocking the active sites and decreasing the availability for propylene polymerization. The experimental data revealed that the presence of furan significantly reduced the productivity of the ZN catalyst by 10, 20, and 41% for concentrations of 6, 12.23, and 25.03 ppm furan, respectively. In addition, a proportional relationship was observed between the furan concentration and the MFI melt index of the polymer, where the higher the furan concentration, the higher the MFI. Likewise, the presence of furan negatively affected the mechanical properties of polypropylene, especially the impact Izod value, with percentage decreases of 9, 18, and 22% for concentrations of 6, 12.23, and 25.03 ppm furan, respectively.12 páginasapplication/pdfengMultidisciplinary Digital Publishing Institute (MDPI)Switzerlandhttps://www.mdpi.com/1422-0067/24/18/14368Experimental–density functional theory (DFT) study of the inhibitory effect of furan residues in the ziegler–natta catalyst during polypropylene synthesisArtículo 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_970fb48d4fbd8a85International journal of molecular sciences1. Bora, R.R.; Wang, R.; You, F. Waste polypropylene plastic recycling toward climate change mitigation and circular economy: Energy, environmental, and technoeconomic perspectives. ACS Sustain. Chem. Eng. 2020, 8, 16350–16363. [CrossRef]2. Alsabri, A.; Tahir, F.; Al-Ghamdi, S.G. Environmental impacts of polypropylene (PP) production and prospects of its recycling in the GCC region. Mater. Today Proc. 2021, 56, 2245–2251. [CrossRef]3. 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]4. Kibria, G.; Masuk, N.I.; Safayet, R.; Nguyen, H.Q.; Mourshed, M. Plastic Waste: Challenges and Opportunities to Mitigate Pollution and Effective Management. Int. J. Environ. Res. 2023, 17, 20. [CrossRef] [PubMed]5. Blazsó, M. Recent trends in analytical and applied pyrolysis of polymers. J. Anal. Appl. Pyrolysis 1997, 39, 1–25. [CrossRef]6. Kruse, T.M.; Wong, H.-W.; Broadbelt, L.J. Mechanistic Modeling of Polymer Pyrolysis: Polypropylene. Macromolecules 2003, 36, 9594–9607. [CrossRef]7. Crews, C.; Castle, L. A review of the occurrence, formation and analysis of furan in heat-processed foods. Trends Food Sci. Technol. 2007, 18, 365–372. [CrossRef]8. Vranová, J.; Ciesarová, Z. Furan in Food-a Review. Czech J. Food Sci. 2009, 27, 1–10. [CrossRef]9. Seok, Y.-J.; Her, J.-Y.; Kim, Y.-G.; Kim, M.Y.; Jeong, S.Y.; Kim, M.K.; Lee, J.-Y.; Kim, C.-I.; Yoon, H.-J.; Lee, K.-G. Furan in Thermally Processed Foods—A Review. Toxicol. Res. 2015, 31, 241–253. [CrossRef]10. Mogol, B.A.; Gökmen, V. Thermal process contaminants: Acrylamide, chloropropanols and furan. Curr. Opin. Food Sci. 2016, 7, 86–92. [CrossRef]11. Gandini, A. The application of the Diels-Alder reaction to polymer syntheses based on furan/maleimide reversible couplings. Polímeros 2005, 15, 95–101. [CrossRef]12. Gandini, A. The behaviour of furan derivatives in polymerization reactions. Adv. Polym. Sci. 1977, 25, 47–96. [CrossRef]13. Hernández-Fernández, J.; Puello-Polo, E.; Márquez, E. Furan as Impurity in Green Ethylene and Its Effects on the Productivity of Random Ethylene–Propylene Copolymer Synthesis and Its Thermal and Mechanical Properties. Polymers 2023, 15, 2264. [CrossRef]14. Pavon, C.; Aldas, M.; Hernández-Fernández, J.; López-Martínez, J. Comparative characterization of gum rosins for their use as sustainable additives in polymeric matrices. J. Appl. Polym. Sci. 2021, 139, 51734. [CrossRef]15. Hernández-Fernández, J.; Guerra, Y.; Espinosa, E. Development and Application of a Principal Component Analysis Model to Quantify the Green Ethylene Content in Virgin Impact Copolymer Resins during Their Synthesis on an Industrial Scale. J. Polym. Environ. 2022, 30, 4800–4808. [CrossRef]16. Cáceres, C.A.C.; Canevarolo, S.V. Correlação entre o Índice de Fluxo à Fusão e a Função da Distribuição de Cisão de Cadeia durante a degradação termo-mecânica do polipropileno. Polímeros 2006, 16, 294–298. [CrossRef]17. Ferg, E.; Bolo, L. A correlation between the variable melt flow index and the molecular mass distribution of virgin and recycled polypropylene used in the manufacturing of battery cases. Polym. Test. 2013, 32, 1452–1459. [CrossRef]18. 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]19. 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]20. Lorenzo, M.L.R. Determinación y Evaluación de las Emisiones de Dioxinas y Furanos en la Producción de Cemento en España. 2008. Available online: https://dialnet.unirioja.es/servlet/tesis?codigo=17310&info=resumen&idioma=SPA (accessed on 5 August 2023).21. Sarra, A.J.; Clave, P. Dioxinas y Furanos Derivados de la Combustión. In Perspectivas; Revista Científica de la Universidad de Belgrano: Buenos Aires, Argentina, 2018; Volume 1. Available online: https://revistas.ub.edu.ar/index.php/Perspectivas/ article/view/15 (accessed on 5 August 2023).22. 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]23. Hernandez-Fernandez, J.; Lambis, H.; Reyes, R.V. Application of Pyrolysis for the Evaluation of Organic Compounds in Medical Plastic Waste Generated in the City of Cartagena-Colombia Applying TG-GC/MS. Int. J. Mol. Sci. 2023, 24, 5397. [CrossRef]24. 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]25. 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]26. 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 2019, 1614, 460736. [CrossRef]27. 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]28. Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Development and validation of a methodology for quantifying partsper-billion levels of arsine and phosphine in nitrogen, hydrogen and liquefied petroleum gas using a variable pressure sampler coupled to gas chromatography-mass spectrometry. J. Chromatogr. A 2021, 1637, 461833. [CrossRef]29. Fernández, J.H.; Cano, H.; Guerra, Y.; Polo, E.P.; Ríos-Rojas, J.F.; Vivas-Reyes, R.; Oviedo, J. Identification and Quantification of Microplastics in Effluents of Wastewater Treatment Plant by Differential Scanning Calorimetry (DSC). Sustainability 2022, 14, 4920. [CrossRef]30. Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Quantification and elimination of substituted synthetic phenols and volatile organic compounds in the wastewater treatment plant during the production of industrial scale polypropylene. Chemosphere 2021, 263, 128027. [CrossRef]31. Hernández-Fernández, J.; Rayón, E.; López, J.; Arrieta, M.P. Enhancing the Thermal Stability of Polypropylene by Blending with Low Amounts of Natural Antioxidants. Macromol. Mater. Eng. 2019, 304, 1900379. [CrossRef]32. Pavon, C.; Aldas, M.; López-Martínez, J.; Hernández-Fernández, J.; Arrieta, M.P. Films Based on Thermoplastic Starch Blended with Pine Resin Derivatives for Food Packaging. Foods 2021, 10, 1171. [CrossRef]33. 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]34. Gómez-Contreras, P.; Figueroa-Lopez, K.J.; Hernández-Fernández, J.; Rodríguez, M.C.; Ortega-Toro, R. Effect of Different Essential Oils on the Properties of Edible Coatings Based on Yam (Dioscorea rotundata L.) Starch and Its Application in Strawberry (Fragaria vesca L.) Preservation. Appl. Sci. 2021, 11, 11057. [CrossRef]35. Chacon, H.; Cano, H.; Fernández, J.H.; Guerra, Y.; Puello-Polo, E.; Ríos-Rojas, J.F.; Ruiz, Y. Effect of Addition of Polyurea as an Aggregate in Mortars: Analysis of Microstructure and Strength. Polymers 2022, 14, 1753. [CrossRef]36. Smith, M.B. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure; John Wiley & Sons: Hoboken, NJ, USA, 202037. Gayatri, G.; Sastry, G.N. Bottlenecks in the prediction of regioselectivity of [4 + 2] cycloaddition reactions: An assessment of reactivity descriptors. J. Chem. Sci. 2005, 117, 573–582. [CrossRef]38. Domingo, L.R.; Picher, M.T.; Sáez, J.A. Toward an understanding of the unexpected regioselective Hetero-Diels-Alder reactions of asymmetric tetrazines with electron-rich ethylenes: A DFT study. J. Org. Chem. 2009, 74, 2726–2735. [CrossRef]39. Parr, R.G.; Gadre, S.R.; Bartolotti, L.J. Local density functional theory of atoms and molecules. Proc. Natl. Acad. Sci. USA 1979, 76, 2522–2526. [CrossRef]40. Parr, R.G.; Yang, W. Density Functional Approach to the Frontier-Electron Theory of Chemical Reactivity. J. Am. Chem. Soc. 1984, 106, 4049–4050. [CrossRef]41. Domingo, L.R.; Aurell, M.; Pérez, P.; Contreras, R. Quantitative characterization of the global electrophilicity power of common diene/dienophile pairs in Diels–Alder reactions. Tetrahedron 2002, 58, 4417–4423. [CrossRef]42. Berkowitz, M.; Parr, R.G. Molecular hardness and softness, local hardness and softness, hardness and softness kernels, and relations among these quantities. J. Chem. Phys. 1988, 88, 2554–2557. [CrossRef]43. Langenaeker, W.; de Proft, F.; Geerlings, P. Development of local hardness-related reactivity indices: Their application in a study of the SE at monosubstituted benzenes within the HSAB context. J. Phys. Chem. 1995, 99, 6424–6431. [CrossRef]44. Chamorro, E.; Chattaraj, P.K.; Fuentealba, P. Variation of the Electrophilicity Index along the Reaction Path. J. Phys. Chem. A 2003, 107, 7068–7072. [CrossRef] [PubMed]45. Pérez, P.; Domingo, L.R.; Duque-Noreña, M.; Chamorro, E. A condensed-to-atom nucleophilicity index. An application to the director effects on the electrophilic aromatic substitutions. J. Mol. Struct. THEOCHEM 2008, 895, 86–91. [CrossRef]46. Fuentealba, P.; Pérez, P.; Contreras, R. On the condensed Fukui function. J. Chem. Phys. 2000, 113, 2544–2551. [CrossRef]47. Neihsial, S.; Lyngdoh, R.D. Novel H-bonded base pairs as potential repeat units for information-bearing macromolecular duplexes: A B3LYP/6-31G∗ search. J. Mol. Struct. THEOCHEM 2007, 806, 213–221. [CrossRef]48. Shubhra, Q.T.H.; Alam, A.K.M.M.; Quaiyyum, M.A. Mechanical properties of polypropylene composites: A review. J. Thermoplast. Compos. Mater. 2011, 26, 362–391. [CrossRef]1211824FuranZiegler–Natta catalystPolypropylene synthesisFlow rateDensity functional theory (DFT)Mechanical propertiesAdsorption affinityPublicationORIGINALExperimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis.pdfExperimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis.pdfapplication/pdf2142432https://repositorio.cuc.edu.co/bitstreams/90bfa7d2-2d42-4f98-8eb6-9cfe2883b489/downloade56b38be0992015287d838dfdb72f396MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-815543https://repositorio.cuc.edu.co/bitstreams/580bbedd-6387-4191-b81c-a17b771ab61f/download73a5432e0b76442b22b026844140d683MD52TEXTExperimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis.pdf.txtExperimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis.pdf.txtExtracted texttext/plain56707https://repositorio.cuc.edu.co/bitstreams/78eeca8d-9378-4eaa-8899-81ec17df23ff/downloaddfae9c09eb67f43dcdd640e660f3d588MD53THUMBNAILExperimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis.pdf.jpgExperimental–Density Functional Theory (DFT) Study of the Inhibitory Effect of Furan Residues in the Ziegler–Natta Catalyst during Polypropylene Synthesis.pdf.jpgGenerated Thumbnailimage/jpeg16338https://repositorio.cuc.edu.co/bitstreams/1149b342-6941-4d9c-9610-aa870ce5bdfd/download3ea5ddffa5674280d25bbb858dd7f2b6MD5411323/13485oai:repositorio.cuc.edu.co:11323/134852024-10-24 03:02:34.238https://creativecommons.org/licenses/by/4.0/©2023 by the authors. Licensee MDPI, Basel, Switzerland.open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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

Publicaciones similares