Kinetic analysis and reaction mechanism of p-alkoxybenzyl alcohol ([4-(hydroxymethyl)phenoxymethyl]polystyrene) resin pyrolysis: Revealing new information on thermal stability
Само за регистроване кориснике
2021
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
This study provides new information on the thermal stability and kinetics of pyrolysis of commonly used resins in solid-phase peptide synthesis. Pyrolysis process of 4-benzyloxybenzyl alcohol resin was monitored by simultaneous TGA-DTG measurements in a nitrogen atmosphere, at four different heating rates (5, 10, 20 and 30 K min(-1)). Kinetic computations included the model-free (isoconversional) and model-based methods for reliable estimation of kinetic parameters and the mechanism of investigated process. Based on the findings from applied methods, the pyrolysis process can be described by three reaction steps, where one of them encompasses the consecutive reactions. The first step (n-th order reaction, referred to Fn) is attributed to the random scission of the main chain in PS (polystyrene) solid support, where polymer radicals were formed. The second step proceeds through homolytic cleavage path of ether linkage of the resin (by the first-order reaction, referred to F1) and then v...ia phenoxy radical (semiquinone) formation which is converted into the benzoquinone through a dehydrogenation (by autocatalysis reaction, referred to Cnm). Finally, the third step (referred to Fn reaction) was characterized by depolymerization mechanism, which takes place at higher temperatures (T > 385 degrees C). With determined kinetic parameters and the most probable mechanism functions, the model agrees excellently with experimental data. By applying the obtained kinetic results, isothermal life-time prediction was also performed.
Кључне речи:
Wang resin / Pyrolysis / Homolytic cleavage / Benzene fragments / AutocatalysisИзвор:
Polymer Degradation and Stability, 2021, 189Издавач:
- Elsevier Sci Ltd, Oxford
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200105 (Универзитет у Београду, Машински факултет) (RS-MESTD-inst-2020-200105)
DOI: 10.1016/j.polymdegradstab.2021.109606
ISSN: 0141-3910
WoS: 000677487900013
Scopus: 2-s2.0-85106255492
Колекције
Институција/група
Mašinski fakultetTY - JOUR AU - Janković, Bojan AU - Manić, Nebojša PY - 2021 UR - https://machinery.mas.bg.ac.rs/handle/123456789/3549 AB - This study provides new information on the thermal stability and kinetics of pyrolysis of commonly used resins in solid-phase peptide synthesis. Pyrolysis process of 4-benzyloxybenzyl alcohol resin was monitored by simultaneous TGA-DTG measurements in a nitrogen atmosphere, at four different heating rates (5, 10, 20 and 30 K min(-1)). Kinetic computations included the model-free (isoconversional) and model-based methods for reliable estimation of kinetic parameters and the mechanism of investigated process. Based on the findings from applied methods, the pyrolysis process can be described by three reaction steps, where one of them encompasses the consecutive reactions. The first step (n-th order reaction, referred to Fn) is attributed to the random scission of the main chain in PS (polystyrene) solid support, where polymer radicals were formed. The second step proceeds through homolytic cleavage path of ether linkage of the resin (by the first-order reaction, referred to F1) and then via phenoxy radical (semiquinone) formation which is converted into the benzoquinone through a dehydrogenation (by autocatalysis reaction, referred to Cnm). Finally, the third step (referred to Fn reaction) was characterized by depolymerization mechanism, which takes place at higher temperatures (T > 385 degrees C). With determined kinetic parameters and the most probable mechanism functions, the model agrees excellently with experimental data. By applying the obtained kinetic results, isothermal life-time prediction was also performed. PB - Elsevier Sci Ltd, Oxford T2 - Polymer Degradation and Stability T1 - Kinetic analysis and reaction mechanism of p-alkoxybenzyl alcohol ([4-(hydroxymethyl)phenoxymethyl]polystyrene) resin pyrolysis: Revealing new information on thermal stability VL - 189 DO - 10.1016/j.polymdegradstab.2021.109606 ER -
@article{ author = "Janković, Bojan and Manić, Nebojša", year = "2021", abstract = "This study provides new information on the thermal stability and kinetics of pyrolysis of commonly used resins in solid-phase peptide synthesis. Pyrolysis process of 4-benzyloxybenzyl alcohol resin was monitored by simultaneous TGA-DTG measurements in a nitrogen atmosphere, at four different heating rates (5, 10, 20 and 30 K min(-1)). Kinetic computations included the model-free (isoconversional) and model-based methods for reliable estimation of kinetic parameters and the mechanism of investigated process. Based on the findings from applied methods, the pyrolysis process can be described by three reaction steps, where one of them encompasses the consecutive reactions. The first step (n-th order reaction, referred to Fn) is attributed to the random scission of the main chain in PS (polystyrene) solid support, where polymer radicals were formed. The second step proceeds through homolytic cleavage path of ether linkage of the resin (by the first-order reaction, referred to F1) and then via phenoxy radical (semiquinone) formation which is converted into the benzoquinone through a dehydrogenation (by autocatalysis reaction, referred to Cnm). Finally, the third step (referred to Fn reaction) was characterized by depolymerization mechanism, which takes place at higher temperatures (T > 385 degrees C). With determined kinetic parameters and the most probable mechanism functions, the model agrees excellently with experimental data. By applying the obtained kinetic results, isothermal life-time prediction was also performed.", publisher = "Elsevier Sci Ltd, Oxford", journal = "Polymer Degradation and Stability", title = "Kinetic analysis and reaction mechanism of p-alkoxybenzyl alcohol ([4-(hydroxymethyl)phenoxymethyl]polystyrene) resin pyrolysis: Revealing new information on thermal stability", volume = "189", doi = "10.1016/j.polymdegradstab.2021.109606" }
Janković, B.,& Manić, N.. (2021). Kinetic analysis and reaction mechanism of p-alkoxybenzyl alcohol ([4-(hydroxymethyl)phenoxymethyl]polystyrene) resin pyrolysis: Revealing new information on thermal stability. in Polymer Degradation and Stability Elsevier Sci Ltd, Oxford., 189. https://doi.org/10.1016/j.polymdegradstab.2021.109606
Janković B, Manić N. Kinetic analysis and reaction mechanism of p-alkoxybenzyl alcohol ([4-(hydroxymethyl)phenoxymethyl]polystyrene) resin pyrolysis: Revealing new information on thermal stability. in Polymer Degradation and Stability. 2021;189. doi:10.1016/j.polymdegradstab.2021.109606 .
Janković, Bojan, Manić, Nebojša, "Kinetic analysis and reaction mechanism of p-alkoxybenzyl alcohol ([4-(hydroxymethyl)phenoxymethyl]polystyrene) resin pyrolysis: Revealing new information on thermal stability" in Polymer Degradation and Stability, 189 (2021), https://doi.org/10.1016/j.polymdegradstab.2021.109606 . .