Thermal decompositions of dialkyl peroxides studied by DSC

Duh, Yih-Shing; Yo, Jin-Min; Lee, Wen-Lian; Kao, Chen-Shan; Hsu, Jing-Ming

doi:10.1007/s10973-014-3998-6

Cited by 20 publications

(14 citation statements)

References 23 publications

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“…This method provides the best fit to experimental data and a heat of reaction

{Δ H}_{2}

of 831 J

\cdot

g −1 (79% of

{Δ H}_{D C P O}

) was found for the principal peak, within the range of

{Δ H}_{D C P O}

reported in . The value of 153.1 kJ

\cdot

mol −1 for the energy of activation is significantly higher than those reported in , between 125 and 139 kJ

\cdot

mol −1 . However Lv et al found a value of energy of activation between 161 and 203 kJ

\cdot

mol −1 using the Friedman isoconvertional method.…”

Section: Resultssupporting

confidence: 64%

“…Actually, an n th ‐order model with coefficients reported in (Table ) is able to properly describe the principal peak occurring in the present experimental results (second peak occurring at higher temperature in Fig. ).…”

Section: Resultssupporting

confidence: 53%

“…The set of parameters A considers that 87% of

{Δ H}_{D C P O}

is due to the second peak. The set of parameters A is within the range of values reported in (Table ) and provides a heat of reaction for the principal peak,

{Δ H}_{2}

, of 904 J

\cdot

g −1 , slightly higher than

{Δ H}_{D C P O}

values reported in .

{\overset{α}{true}}_{D C P O} = k_{1} \cdot e^{\frac{- E_{1}}{R T}} \cdot {(1 - ζ - α_{1})}^{n_{1}} + k_{2} \cdot e^{\frac{- E_{2}}{R T}} \cdot {(ζ - α_{2})}^{n_{2}}

…”

Section: Resultsmentioning

confidence: 78%

“…The nature of both peaks was not further investigated in the present study. It is noteworthy that a weak secondary peak has been neglected in .…”

Section: Resultsmentioning

confidence: 99%

“…). Starting from the parameters reported in (Table ) and assuming a pseudo first‐order model for the second peak, a first set of parameters, labeled A, has been identified to fit the present experimental data with two uncoupled n th ‐order model ( Eq . ), each related to a part of the total heat of reaction (

ζ

for the second peak and

(|, 1 - ζ)

for the first one).…”

Section: Resultsmentioning

confidence: 99%

See 4 more Smart Citations

Effect of dicumyl peroxide concentration on the polymerization kinetics of a polysilazane system

D׳Elia

Dusserre

Confetto

et al. 2017

Polymer Engineering & Sci

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The effect of dicumyl peroxide (DCPO) concentration on the polymerization kinetics of a polysilazane system has been investigated through DSC analyses. DCPO acts as polymerization initiator by activating the polyaddition of vinyl groups. The overall heat of reaction is found to be a linear function of the DCPO concentration above 1.5 wt%, due to the addition of the heat of fully initiated polymerization and the heat of DCPO decomposition. Below 1.5 wt% of DCPO, the polymerisation of polysilazane is not fully initiated and only part of the reaction occurs. The resulting overall heat of reaction is therefore lower than that provided by the linear law valid for higher concentrations. A two-reaction kinetic model built on this interpretation leads to a satisfactory representation of the DSC analyses performed for each DCPO concentration between 0.1 and 20 wt%. POLYM. ENG. SCI., 58:859-869, 2018.

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“…This method provides the best fit to experimental data and a heat of reaction

{Δ H}_{2}

of 831 J

\cdot

g −1 (79% of

{Δ H}_{D C P O}

) was found for the principal peak, within the range of

{Δ H}_{D C P O}

reported in . The value of 153.1 kJ

\cdot

mol −1 for the energy of activation is significantly higher than those reported in , between 125 and 139 kJ

\cdot

mol −1 . However Lv et al found a value of energy of activation between 161 and 203 kJ

\cdot

mol −1 using the Friedman isoconvertional method.…”

Section: Resultssupporting

confidence: 64%

Section: Resultssupporting

confidence: 53%

“…The set of parameters A considers that 87% of

{Δ H}_{D C P O}

is due to the second peak. The set of parameters A is within the range of values reported in (Table ) and provides a heat of reaction for the principal peak,

{Δ H}_{2}

, of 904 J

\cdot

g −1 , slightly higher than

{Δ H}_{D C P O}

values reported in .

{\overset{α}{true}}_{D C P O} = k_{1} \cdot e^{\frac{- E_{1}}{R T}} \cdot {(1 - ζ - α_{1})}^{n_{1}} + k_{2} \cdot e^{\frac{- E_{2}}{R T}} \cdot {(ζ - α_{2})}^{n_{2}}

…”

Section: Resultsmentioning

confidence: 78%

“…The nature of both peaks was not further investigated in the present study. It is noteworthy that a weak secondary peak has been neglected in .…”

Section: Resultsmentioning

confidence: 99%

ζ

for the second peak and

(|, 1 - ζ)

for the first one).…”

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Effect of dicumyl peroxide concentration on the polymerization kinetics of a polysilazane system

D׳Elia

Dusserre

Confetto

et al. 2017

Polymer Engineering & Sci

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Calorimetric Approaches to Characterizing Undesired Reactions

Roth

2019

Chemical Engineering in the Pharmaceutical Industry

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Measurement and modeling of peroxides half‐life: A thermo‐kinetic approach

Dan,

Bagaria,

Habersberger

et al. 2023

Int J of Chemical Kinetics

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Half‐life values of organic peroxides at elevated temperature conditions are important in characterizing the reactivity and are often available in literature or through vendors. However, there is often lack of details/accuracy on methods used to obtain these values, as well as differences in methods across vendors and publications, thus resulting in discrepant reactivity profile. To address this, a method involving calorimetric experiment and thermo‐kinetic modeling was developed. The current approach was applied on five peroxides samples to obtain kinetic parameters and estimate their half‐life in the temperature range of interest. The measurements were performed by DSC under non‐isothermal conditions on the dilute peroxide solutions (∼0.12 M in mineral oil) and the data were kinetically treated according to three model‐based and one model‐free kinetic equations. A very good agreement was found between the half‐life calculated by all kinetic methods, but significant differences were noticed with the kinetic parameters reported in literature. Additionally, the obtained half‐life results, based on non‐isothermal measurements developed kinetic models, were validated through isothermal calorimetric testing. Given the accuracy and robustness of our results, the current method can be applied to estimate half‐life of organic peroxides at elevated temperature conditions.

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Thermal decompositions of dialkyl peroxides studied by DSC

Cited by 20 publications

References 23 publications

Effect of dicumyl peroxide concentration on the polymerization kinetics of a polysilazane system

Effect of dicumyl peroxide concentration on the polymerization kinetics of a polysilazane system

Calorimetric Approaches to Characterizing Undesired Reactions

Measurement and modeling of peroxides half‐life: A thermo‐kinetic approach

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