Kinetic studies on thermal decomposition of polystyrene peroxide

Kishore, K.; Verneker, V. R. Pai; Gayathri, V.

doi:10.1016/0165-2370(80)80015-5

Cited by 6 publications

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“…We demonstrate the strength of pairing kMC modeling and AI for the thermal degradation of poly(styrene peroxide) as its degradation initiation mechanism is fast and literature data on overall characteristics are available. , As shown in Figure , considering PSP as defined by P 12 , peroxide bonds break first to onset degradation and, hence, the initiation step is well defined. − This makes PSP an excellent candidate to gain an understanding of what the dominant pathways for the formation of major and minor products during pyrolysis are. PSP belongs to a family of materials called polyperoxides, which incorporate multiple peroxide bonds in their polymeric backbone .…”

Section: Introductionmentioning

confidence: 86%

“…The pyrolysis of PSP has been studied experimentally by Kishore and co-workers as well. − ,− These authors used differential scanning calorimetry (DSC) to report an exothermic decomposition around 100 °C, which is a characteristic of peroxide bond breakage . Kishore and Ravindran calculated the heat of degradation as ca.…”

Section: Introductionmentioning

confidence: 99%

“…210 kJ mol –1 assuming only the formation of benzaldehyde and formaldehyde . Additionally, Kishore et al calculated the (overall) apparent activation energy for PSP pyrolysis using both DSC and thermogravimetric analysis (TGA) as 126 kJ mol –1 . They stated that this value is plausible since the bond dissociation energy for a peroxide bond is reported as 134 kJ mol –1 and the rate-controlling step in PSP pyrolysis is presumably the cleavage of the peroxide bond. , Furthermore, high-temperature (430 °C) thermal degradation of PSP using pyrolysis-gas chromatography (Py-GC) demonstrated that the major pyrolysis products are benzaldehyde and formaldehyde in equimolar quantities so that the product distribution does not change significantly over the wide temperature range of 100–450°C.…”

Section: Introductionmentioning

confidence: 99%

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Distribution Changes during Thermal Degradation of Poly(styrene peroxide) by Pairing Tree-Based Kinetic Monte Carlo and Artificial Intelligence Tools

Dogu

Plehiers

Vijver

et al. 2021

Ind. Eng. Chem. Res.

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A tree-based kinetic Monte Carlo (kMC) model is presented that differentiates between 38 end-group pairs for isothermal degradation of poly(styrene peroxide) (PSP). The binary trees allow for fast and accurate calculation of reaction probabilities, with mass-weighted binary trees for the accurate sampling of peroxide bond fissions and hydrogen abstractions along chains. The kinetic parameters are tuned via artificial neural networks (ANNs) to successfully predict literature experimental data, among other lumped product yields. ANNs are also utilized for sensitivity analysis to unravel the effects of individual reactions on the time evolution of experimental responses and other simulation outputs, including the variations of the chain length distributions of the macrospecies. PSP degradation is characterized by three stages of degradation considering both instantaneous and time-averaged concentrations. The first stage features rapid unzipping and results in the fast production of major products benzaldehyde and formaldehyde, the second stage features the most significant level of hydrogen abstractions involving PSP and other macrospecies types, and the third stage exhibits the consumption of the remaining peroxide bonds toward oligomeric species in a wide time frame until the degradation process is finalized by the depletion of peroxide bonds. This proof-of-concept study based on unprecedentedly detailed analyses of the chemistry via kinetic Monte Carlo paves the way to further improve our understanding of chemical recycling of solid plastic waste.

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Section: Introductionmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Distribution Changes during Thermal Degradation of Poly(styrene peroxide) by Pairing Tree-Based Kinetic Monte Carlo and Artificial Intelligence Tools

Dogu

Plehiers

Vijver

et al. 2021

Ind. Eng. Chem. Res.

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“…Further, the kinetics of PSP decomposition have been studied by isothermal thermogravimetry (TG) [2]. The activation energy (E) was found to be 136 kJ mole -1 and it was suggested that the rate-controlling step is -O-Obond dissociation [2].…”

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confidence: 99%

Mechanism of the thermal decomposition of polystyrene peroxide

Kishore

1981

Journal of Thermal Analysis

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The thermal degradation of polystyrene peroxide was carried out using differential scanning calorimetry. The activation energy (E) was found to be 136 kJ mole -1 at all extents of decomposition. The E value was found to correspond to --O-O--dissociation. The order of reaction was found to decrease from 2 to 1 as the decomposition progresses, and the mechanism of the changeover was explained.The nuclear magnetic resonance spectra (NMR), differential thermal analysis (DTA) and differential scanning calorimetric (DSC) analysis of pure polystyrene (PSP) have recently been reported [1 ]. Further, the kinetics of PSP decomposition have been studied by isothermal thermogravimetry (TG) [2]. The activation energy (E) was found to be 136 kJ mole -1 and it was suggested that the rate-controlling step is -O-Obond dissociation [2]. The order of reaction (n) and the detailed mechanism for pure PSP decomposition have not been reported so far.It has been shown that DSC can be used to study the kinetics of the process and that E can be derived without recourse to kinetic assumptions [3]. PSP decomposition was carried out by using the DSC technique (Perkin-Elmer DSC-1B), and the kinetic parameters such as E and n were evaluated to understand the mechanism.The details of the operation of the instrument and the derivation of the fraction decomposed (ct) vs. time (t) or vs. temperature (T) plots from the thermal curves are described elsewhere [3]. Thermal curves obtained in the scanning modes were used for kinetic analysis. The shapes of the DSC curves of PSP can be seen elsewhere [1 ].E was calculated by using the following equation :where S is the DSC signal in millicalories per second for full-scale deflection, AH is the total heat of PSP decomposition, A is the frequency factor and R is the S 1 gas constant. From Eq. (1), E was obtained by plotting In ~ vs. -~. In doing so, and n were kept constant, a was fixed at a definite value for the curves at different heating rates, and the constancy of n was checked from the reduced-time plots

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