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
The copolymer synthesis process can be affected by failures in the production process or by contaminating compounds such as ketones, thiols, and gases, among others. These impurities act as an inhibiting agent of the Ziegler–Natta (ZN) catalyst affecting its productivity and disturbing the polymeriz...
- Autores:
-
Hernández Fernández, Joaquín
Ortega-Toro, Rodrigo
Castro-Suarez, John R.
- 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:11323/10477
- Acceso en línea:
- https://hdl.handle.net/11323/10477
https://repositorio.cuc.edu.co/
- Palabra clave:
- Formaldehyde–propionaldehyde and butyraldehyde
Green ethylene
Ziegler–Natta
Polypropylene
Catalyst
Degradation
Random copolymer
- Rights
- openAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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| dc.title.eng.fl_str_mv |
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 |
| title |
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 |
| spellingShingle |
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 Formaldehyde–propionaldehyde and butyraldehyde Green ethylene Ziegler–Natta Polypropylene Catalyst Degradation Random copolymer |
| title_short |
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 |
| title_full |
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 |
| title_fullStr |
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 |
| title_full_unstemmed |
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 |
| title_sort |
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 |
| dc.creator.fl_str_mv |
Hernández Fernández, Joaquín Ortega-Toro, Rodrigo Castro-Suarez, John R. |
| dc.contributor.author.none.fl_str_mv |
Hernández Fernández, Joaquín Ortega-Toro, Rodrigo Castro-Suarez, John R. |
| dc.subject.proposal.eng.fl_str_mv |
Formaldehyde–propionaldehyde and butyraldehyde Green ethylene Ziegler–Natta Polypropylene Catalyst Degradation Random copolymer |
| topic |
Formaldehyde–propionaldehyde and butyraldehyde Green ethylene Ziegler–Natta Polypropylene Catalyst Degradation Random copolymer |
| description |
The copolymer synthesis process can be affected by failures in the production process or by contaminating compounds such as ketones, thiols, and gases, among others. These impurities act as an inhibiting agent of the Ziegler–Natta (ZN) catalyst affecting its productivity and disturbing the polymerization reaction. In this work, the effect of formaldehyde, propionaldehyde, and butyraldehyde on the ZN catalyst and the way in which it affects the final properties of the ethylene-propylene copolymer is presented by analyzing 30 samples with different concentrations of the mentioned aldehydes along with three control samples. It was determined that the presence of formaldehyde 26 ppm, propionaldehyde 65.2 ppm, and butyraldehyde 181.2 ppm considerably affect the productivity levels of the ZN catalyst; this effect increases as the concentration of aldehydes is higher in the process; likewise, these impurities affect the properties of the final product, such as the fluidity index (MFI), thermogravimetric analysis (TGA), bending, tension, and impact, which leads to a polymer with low-quality standards and less resistance to breakage. The computational analysis showed that the complexes formed by formaldehyde, propionaldehyde, and butyraldehyde with the active center of the catalyst are more stable than those obtained by the ethylene-Ti and propylene-Ti complexes, presenting values of −40.5, −47.22, −47.5, −5.2 and −1.3 kcal mol−1 respectively |
| publishDate |
2023 |
| dc.date.accessioned.none.fl_str_mv |
2023-09-11T19:11:48Z |
| dc.date.available.none.fl_str_mv |
2023-09-11T19:11:48Z |
| dc.date.issued.none.fl_str_mv |
2023-02-22 |
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Artículo de revista |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
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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. https://doi.org/10.3390/ polym15051098 |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/10477 |
| dc.identifier.doi.none.fl_str_mv |
10.3390/polym15051098 |
| dc.identifier.eissn.spa.fl_str_mv |
2073-4360 |
| dc.identifier.instname.spa.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.spa.fl_str_mv |
REDICUC - Repositorio CUC |
| dc.identifier.repourl.spa.fl_str_mv |
https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
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. https://doi.org/10.3390/ polym15051098 10.3390/polym15051098 2073-4360 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
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https://hdl.handle.net/11323/10477 https://repositorio.cuc.edu.co/ |
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eng |
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eng |
| dc.relation.ispartofjournal.spa.fl_str_mv |
Polymers |
| dc.relation.references.spa.fl_str_mv |
1. Fan, D.; Dai, D.J.; Wu, H.S. Ethylene formation by catalytic dehydration of ethanol with industrial considerations. Materials 2012, 6, 101–115. [CrossRef] 2. 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] 3. Penteado, A.T.; Kim, M.; Godini, H.R.; Esche, E.; Repke, J.U. Biogas as a renewable feedstock for green ethylene production via oxidative coupling of methane: Preliminary feasibility study. Chem. Eng. Trans. 2017, 61, 589–594. 4. Abril, A.; Navarro, E.A. Etanol a Partir de Biomasa Lignocelulósica; Aleta: Valencia, Spain, 2012; pp. 46–47. 5. Himmelmann, R.; Otterstaetter, R.; Franke, O.; Brand, S.; Wachsen, O.; Mestl, G.; Efenberger, F.; Klemm, E. Selective oxidation of ethanol to ethylene oxide with a dual-layer concept. Catal. Commun. 2022, 167, 106424. [CrossRef] 6. Hu, Y.S.; Kamdar, A.R.; Ansems, P.; Chum, S.P.; Hiltner, A.; Baer, E. Crystallization of a miscible propylene/ethylene copolymer blend. Polymer 2006, 47, 6387–6397. [CrossRef] 7. Du, Z.X.; Xu, J.T.; Dong, Q.; Fan, Z.Q. Thermal fractionation and efect of comonomer distribution on the crystal structure of ethylene-propylene copolymers. Polymer 2009, 50, 2510–2515. [CrossRef] 8. Jermolovicius, L.A.; Pouzada, E.V.S.; Do Nascimento, R.B.; de Castro, E.R.; Senise, J.T.; Mente, B.B.; Martins, M.C.; Yamaguchi, S.M.; Sanchez, V.C. Greening the green ethylene with microwaves. Chem. Eng. Process 2018, 127, 238–248. [CrossRef] 9. Wang, Z.; Shi, R.; Zhang, T. Three-phase electrochemistry for green ethylene production. Curr. Opin. Electroche. 2021, 30, 100789. [CrossRef] 10. Fernández, A.; Expósito, M.T.; Peña, B.; Berger, R.; Shu, J.; Graf, R.; Spiess, H.W.; García-Muñoz, R.A. Molecular structure and local dynamic in impact polypropylene copolymers studied by preparative TREF, solid state NMR spectroscopy, and SFM microscopy. Polymer 2015, 61, 87–98. [CrossRef] 11. 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 Im-provement of their Durability in Multiple Applications. J. Polym. Environ. 2023, 1–10. [CrossRef] 12. 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] 13. Nikolaeva, M.; Mikenas, T.; Matsko, M.; Zakharov, V. Effect of AlEt3 and an External Donor on the Distribution of Active Sites According to Their Stereospecificity in Propylene Polymerization over TiCl4/MgCl2 Catalysts with Different Titanium Content. Macromol. Chem. Phys. 2016, 217, 1384–1395. [CrossRef] 14. Bahri-Laleh, N. Interaction of Different Poisons with MgCl2/TiCl4 Based Ziegler-Natta Catalysts. Appl. Surf. Sci. 2016, 379, 395–401. [CrossRef] 15. Hernández Fernández, J.A. Uso de Aditivos Sostenibles en la Estabilización Térmica del Polipropileno en su Proceso de Síntesis (Doctoral dissertation, Universitat Politècnica de València). Ph.D. Thesis, Universitat Politècnica de València, Alcoy, España, 2018. 16. Hernández-Fernández, J. Quantifcation of oxygenates, sulphides, thiols and permanent gases in propylene: A multiple linear regression model to predict the loss of efciency in polypropylene production on an industrial scale. J. Chromatogr. A 2020, 1628, 461478. [CrossRef] 17. Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A. 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] 18. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.A.; et al. The Effects of Oxidation States, Spin States and Solvents on Molecular Structure, Stability and Spectroscopic Properties of Fe-Catechol Complexes: A Theoretical Study. Adv. Chem. Eng. Sci. 2017, 7, 137–153. 19. Ernzerhof, M.; Perdew, J. Generalized gradient approximation to the angleand system-averaged exchange hole. J. Chem. Phys. 1998, 109, 3313. [CrossRef] 20. Schäfer, C.; Ahlrichs, H.R. Fully optimized contracted gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J. Chem. Phys. 1994, 100, 5829–5835. [CrossRef] 21. Correa, A.; Piemontesi, F.; Morini, G.; Cavallo, L. Key elements in the structure and function relationship of the MgCl2/TiCl4/Lewis base Ziegler-Natta catalytic system. Macromolecules 2007, 40, 9181–9189. [CrossRef] 22. Choudhary, K.D.; Nayyar, A.; Dasgupta, M.S. Effect of Compression Ratio on Combustion and Emission Characteristics of C.I. Engine Operated with Acetylene in Conjunction with Diesel Fuel. Fuel 2018, 214, 489–496. [CrossRef] 23. Davis, T.E.; Tobias, R.L.; Peterli, E.B. Thermal Degradation of Polypropylene. J. Polym. Sci. 1962, 56, 485–499. [CrossRef] 24. Hernández-Fernández, J.; Rodriguez, E. Dermination of phenolic antioxidants additives in industrial wastewater from polypropylene production using soild phase extraction with high-performance liquid chromatography. J. Chromatogr. A 2010, 1607, 460442. [CrossRef] 25. Hernández Fernández, J.; Rayon, E.; Lopez, J.; Arrieta, M. Enchancing the termal stability of polypropylene by blending with low amounts of natural antioxidants. Macromol. Mater. Eng. 2019, 304, 1900379. [CrossRef] 26. 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. Chemosphere 2021, 263, 128027. [CrossRef] 27. Hernández Fernández, J.; Lopez, J. Quantification pf poisons for Ziegler Natta Catalysts and effects on the production of polypropylene by gas chromatographic with simultaneous detection: Pulsed discharge helium. J. Chromatogr. A 2020, 1614, 460736. 28. Hernández-Fernández, J. Quantification of arsine and phosphine in industrial atmospheric emissions in Spain and Colombia. Implementation of modified zeolites to reduce the environmental impact of emissions. Atmos. Pollut. Res. 2021, 12, 167–176. [CrossRef] 29. Hernández-Fernández, J. Films Base don Thermoplastic Starch Blended with Pine Resin Derivatives for Food Packaging. Foods 2021, 10, 1171. 30. Bonachela, S.; Lopez, J.; Granados, M.; Magan, J.; Hernandez, J.; Baille, A. Effects of gravel mulch on surface energy balance and soil termal regime in an unheated plastic Greenhouse. Biosyst. Eng. 2020, 192, 1–13. [CrossRef] 31. Hernández-Fernández, J.; Lopez, J. Experimental study of the autocatalytic effect of triethylaluminum and TiCl4 residuals at the onset of nonadditive polypropylene degradation and their impacto n thermo-oxidative degradation and pyrolysis. J. Anal. Appl. Pyrolysis 2021, 155, 105052. [CrossRef] 32. Hernández-Fernández, J.; Martinez, J. Autocatalytic influence of different levels of arsin o the termal stability and pyrolysis of polypropylene. J. Anal. Appl. Pyrolysis 2022, 161, 105385. 33. Hernández-Fernández, J.; Lopez Martinez, J.; Barceló, D. Development and validation of a methodology for quantifying part-perbillion levels opf arsine and phosphine in nitrogen, hydrogen and liquefied petroleum gas using a variable. J. Chromatogr. A 2021, 1637, 461833. [CrossRef] 34. Hernández-Fernández, J. Effects of Different Concentrations of Arsine on the Synthesis and Final Properties of polypropylene. Polymers 2022, 14, 3132. [CrossRef] 35. Hernández-Fernández, J.; Guerra, Y.; Puello-Polo, E.; Marquez, E. Identification and Quantification of Microplastics in Effluents of Wastewater Treatment Plant by Differential Scanning Calorimetry (DSC). Sustainability 2022, 14, 4920. [CrossRef] 36. Hernández-Fernández, J. Comparative Characterization of gum rosins for their use as sustainable additives in polymeric matrices. J. Appl. Polym. Sci. 2021, 14, 4920. 37. Hernandez-Fernandez, J.; Cano, H.; Guerra, Y. Detection of Bisphenol A and Four Analogues in Atmospheric Emissions in Petrochemical Complexes Producing Polypropylene in South America. Molecules 2022, 27, 4832. [CrossRef] 38. Chacon, H.; Cano, H.; Hernandez, J.; Guerra, Y.; Puello Polo, E.; Rio 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] |
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© 2023 by the authors. Licensee MDPI, Basel, Switzerland. |
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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. Licensee MDPI, Basel, Switzerland.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Hernández Fernández, JoaquínOrtega-Toro, RodrigoCastro-Suarez, John R.2023-09-11T19:11:48Z2023-09-11T19:11:48Z2023-02-22Hernández-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. https://doi.org/10.3390/ polym15051098https://hdl.handle.net/11323/1047710.3390/polym150510982073-4360Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/The copolymer synthesis process can be affected by failures in the production process or by contaminating compounds such as ketones, thiols, and gases, among others. These impurities act as an inhibiting agent of the Ziegler–Natta (ZN) catalyst affecting its productivity and disturbing the polymerization reaction. In this work, the effect of formaldehyde, propionaldehyde, and butyraldehyde on the ZN catalyst and the way in which it affects the final properties of the ethylene-propylene copolymer is presented by analyzing 30 samples with different concentrations of the mentioned aldehydes along with three control samples. It was determined that the presence of formaldehyde 26 ppm, propionaldehyde 65.2 ppm, and butyraldehyde 181.2 ppm considerably affect the productivity levels of the ZN catalyst; this effect increases as the concentration of aldehydes is higher in the process; likewise, these impurities affect the properties of the final product, such as the fluidity index (MFI), thermogravimetric analysis (TGA), bending, tension, and impact, which leads to a polymer with low-quality standards and less resistance to breakage. The computational analysis showed that the complexes formed by formaldehyde, propionaldehyde, and butyraldehyde with the active center of the catalyst are more stable than those obtained by the ethylene-Ti and propylene-Ti complexes, presenting values of −40.5, −47.22, −47.5, −5.2 and −1.3 kcal mol−1 respectively15 páginasapplication/pdfengMDPI AGSwitzerlandhttps://www.mdpi.com/2073-4360/15/5/1098Theoretical–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 copolymerArtículo 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_970fb48d4fbd8a85Polymers1. Fan, D.; Dai, D.J.; Wu, H.S. Ethylene formation by catalytic dehydration of ethanol with industrial considerations. Materials 2012, 6, 101–115. [CrossRef]2. 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]3. Penteado, A.T.; Kim, M.; Godini, H.R.; Esche, E.; Repke, J.U. Biogas as a renewable feedstock for green ethylene production via oxidative coupling of methane: Preliminary feasibility study. Chem. Eng. Trans. 2017, 61, 589–594.4. Abril, A.; Navarro, E.A. Etanol a Partir de Biomasa Lignocelulósica; Aleta: Valencia, Spain, 2012; pp. 46–47.5. Himmelmann, R.; Otterstaetter, R.; Franke, O.; Brand, S.; Wachsen, O.; Mestl, G.; Efenberger, F.; Klemm, E. Selective oxidation of ethanol to ethylene oxide with a dual-layer concept. Catal. Commun. 2022, 167, 106424. [CrossRef]6. Hu, Y.S.; Kamdar, A.R.; Ansems, P.; Chum, S.P.; Hiltner, A.; Baer, E. Crystallization of a miscible propylene/ethylene copolymer blend. Polymer 2006, 47, 6387–6397. [CrossRef]7. Du, Z.X.; Xu, J.T.; Dong, Q.; Fan, Z.Q. Thermal fractionation and efect of comonomer distribution on the crystal structure of ethylene-propylene copolymers. Polymer 2009, 50, 2510–2515. [CrossRef]8. Jermolovicius, L.A.; Pouzada, E.V.S.; Do Nascimento, R.B.; de Castro, E.R.; Senise, J.T.; Mente, B.B.; Martins, M.C.; Yamaguchi, S.M.; Sanchez, V.C. Greening the green ethylene with microwaves. Chem. Eng. Process 2018, 127, 238–248. [CrossRef]9. Wang, Z.; Shi, R.; Zhang, T. Three-phase electrochemistry for green ethylene production. Curr. Opin. Electroche. 2021, 30, 100789. [CrossRef]10. Fernández, A.; Expósito, M.T.; Peña, B.; Berger, R.; Shu, J.; Graf, R.; Spiess, H.W.; García-Muñoz, R.A. Molecular structure and local dynamic in impact polypropylene copolymers studied by preparative TREF, solid state NMR spectroscopy, and SFM microscopy. Polymer 2015, 61, 87–98. [CrossRef]11. 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 Im-provement of their Durability in Multiple Applications. J. Polym. Environ. 2023, 1–10. [CrossRef]12. 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]13. Nikolaeva, M.; Mikenas, T.; Matsko, M.; Zakharov, V. Effect of AlEt3 and an External Donor on the Distribution of Active Sites According to Their Stereospecificity in Propylene Polymerization over TiCl4/MgCl2 Catalysts with Different Titanium Content. Macromol. Chem. Phys. 2016, 217, 1384–1395. [CrossRef]14. Bahri-Laleh, N. Interaction of Different Poisons with MgCl2/TiCl4 Based Ziegler-Natta Catalysts. Appl. Surf. Sci. 2016, 379, 395–401. [CrossRef]15. Hernández Fernández, J.A. Uso de Aditivos Sostenibles en la Estabilización Térmica del Polipropileno en su Proceso de Síntesis (Doctoral dissertation, Universitat Politècnica de València). Ph.D. Thesis, Universitat Politècnica de València, Alcoy, España, 2018.16. Hernández-Fernández, J. Quantifcation of oxygenates, sulphides, thiols and permanent gases in propylene: A multiple linear regression model to predict the loss of efciency in polypropylene production on an industrial scale. J. Chromatogr. A 2020, 1628, 461478. [CrossRef]17. Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A. 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]18. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.A.; et al. 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[CrossRef]151515Formaldehyde–propionaldehyde and butyraldehydeGreen ethyleneZiegler–NattaPolypropyleneCatalystDegradationRandom copolymerPublicationORIGINALTheoretical–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.pdfTheoretical–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.pdfArtículoapplication/pdf3002705https://repositorio.cuc.edu.co/bitstreams/7eb697c1-34ee-458d-90ed-c0e0db733454/download98e4e3744066859fe01c9a693ab0adfbMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/15a055f1-5e9e-43f7-ac22-622dcf4993f6/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTTheoretical–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.pdf.txtTheoretical–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.pdf.txtExtracted texttext/plain53118https://repositorio.cuc.edu.co/bitstreams/8b1e29e8-268f-4169-85d7-5d5346558b15/download9af362abc5751da496b38ff72dbbd796MD53THUMBNAILTheoretical–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.pdf.jpgTheoretical–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.pdf.jpgGenerated Thumbnailimage/jpeg16784https://repositorio.cuc.edu.co/bitstreams/088a94a5-f08d-44c4-b092-4d99d3624885/downloadaeeb47e2f8067d4bd135d1a4ead0cff3MD5411323/10477oai:repositorio.cuc.edu.co:11323/104772024-09-17 10:57:31.353https://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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