Dicumyl Peroxide Thermal Decomposition in Cumene: Development of a Kinetic Model

Somma, Ilaria Di; Marotta, Raffaele; Andreozzi, Roberto; Caprio, V.

doi:10.1021/ie201659a

Cited by 25 publications

(17 citation statements)

References 12 publications

(14 reference statements)

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“…A higher amount of gel fraction with DCP compared to that with BPO was already identified in other studies. , Indeed, DCP is the most frequently used cross-linking agent since it is an organic peroxide which is more selective to vinyl moieties than benzoyl peroxide. , The ability of the cumyloxy radical from DCP to react with nonactivated vinyl moieties in a free-radical cross-linking pathway via H abstraction may be a possible explanation of its higher reactivity compared to BPO . Additionally, the cumyloxy radical can undergo β-scission resulting in radical fragments (methyl radical and acetophenone) with high mobility . Furthermore, the unsaturated bonds are not easily accessible by benzoyloxy radicals due to the steric hindrance around double bonds with the increased formation of cross-linked networks .…”

Section: Resultsmentioning

confidence: 82%

“…35 Additionally, the cumyloxy radical can undergo βscission resulting in radical fragments (methyl radical and acetophenone) with high mobility. 36 Furthermore, the unsaturated bonds are not easily accessible by benzoyloxy radicals due to the steric hindrance around double bonds with the increased formation of cross-linked networks. 29 The SEC analysis of the BPO soluble fraction testified to the presence of oligomers (see Figure S7, M n = 320 g•mol −1 , Đ = 1.5) which indicated that some polymer backbone cleavage also takes place during the cross-linking.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Caryophyllene as a Precursor of Cross-Linked Materials

Medeiros

Coz

Grau

2020

ACS Sustainable Chem. Eng.

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This paper aims at the synthesis of a new type of elastomers from caryophyllene. The adopted strategy was to cross-link the polycaryophyllene, which was synthesized by ring-opening metathesis polymerization (ROMP). The polycaryophyllene obtained showed Mn = 2 x 10 4 g.mol-1 (Đ = 1.5) with a glass transition temperature (Tg) of-35 °C. On the first hand, thermal cross-linking was performed in the presence of organic peroxides or sulfur system. On the second hand, thiol-ene coupling initiated by UV-light at room temperature was also investigated as an alternative pathway to cross-link the polycaryophyllene. The materials obtained were analyzed by TGA, DSC, and DMA. The Tg of cross-linked polycaryophyllene could be easily modulated from-35 °C to a range between-25 and 10 °C by changing the type of cross-linking agent. The curing process led to the improvement of thermal stability ranging from 200 °C to around 340 °C. Finally, the network storage modulus varied from 1 to 100 MPa at room temperature.

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Section: Resultsmentioning

confidence: 82%

Section: ■ Results and Discussionmentioning

confidence: 99%

Caryophyllene as a Precursor of Cross-Linked Materials

Medeiros

Coz

Grau

2020

ACS Sustainable Chem. Eng.

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“…A better description of the whole kinetics would necessitate studying separately the two mechanisms by carrying out a coupled approach, involving an identification of the polymerization parameters once the degradation has been described with another phenomenological model. A larger amount of work would be necessary to build a mechanistic approach, since the degradation of dicumyl peroxide, alone, involves about 50 reactions [41].…”

Section: Cure Kinetics Modellingmentioning

confidence: 99%

Cure kinetics of a polysilazane system: Experimental characterization and numerical modelling

D׳Elia

Dusserre

Confetto

et al. 2016

European Polymer Journal

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The Time-Temperature-Transformation (TTT) isothermal diagram is plotted for a polysilazane system, composed of the KiON Ò Ceraset Ò Polysilazane 20 resin, with addition of 1 wt% of dicumyl peroxide acting as cross-linking catalyst. This diagram is useful to control the resin transfer moulding (RTM) process involved to obtain a composite material from a ceramic fibrous preform. The system under study is a precursor for the ceramic matrix, obtained after pyrolysis of the polymerized resin. The knowledge of the composite properties at the polymerized state is necessary to fully control this process. The cure kinetics of this system is investigated under both isothermal and dynamic curing conditions by Differential Scanning Calorimetry (DSC). The kinetics of the reaction is satisfactorily described by a Kamal and Sourour (K-S) phenomenological model. The K-S parameters are identified from isothermal data, taking into account an initial degree of cure, assuming a fully cured system at the end of the isothermal idle time. The model is in good agreement with both dynamic and isothermal experimental data. The glass transition temperature (T g) is determined by DSC analyses as a function of the degree of polymerization and confirmed by Dynamic Mechanical Analysis (DMA), and the results are modelled by Di Benedetto's formula. The change of visco-elastic properties is investigated using oscillatory rheology under isothermal conditions. The cure kinetics model allows a gelation criterion to be identified by plotting the shear loss modulus G 00 vs. the degree of cure.

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“…30 Additionally, the cumyloxy radical can undergo β-scission resulting in radical fragments (methyl radical and acetophenone) with high mobility. 31 Furthermore, the unsaturated bonds are not easily accessible by benzoyloxy radicals due to the steric hindrance around double bonds as the increase of formation of cross-linked networks. 24 The SEC analysis of the BPO soluble fraction testified to the presence of oligomers (see Fig.…”

Section: Introductionmentioning

confidence: 99%

Caryophyllene as a Precursor of Cross-Linked Materials

Medeiros¹,

Coz²,

Grau

2019

Preprint

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This paper aims at the synthesis of a new type of elastomers from caryophyllene. The adopted strategy was to cross-link the polycaryophyllene, which was synthesized by ring-opening metathesis polymerization (ROMP). The polycaryophyllene obtained showed Mn = 2 x 104 g.mol-1 (Đ = 1.5) with a glass transition temperature (Tg) of -35 °C. On the first hand, thermal crosslinking was performed in the presence of organic peroxides or sulfur system. On the second hand, thiol-ene coupling initiated by UV-light at room temperature was also investigated as an alternative pathway to cross-link the polycaryophyllene. The materials obtained were analyzed by TGA, DSC, and DMA. The Tg of cross-linked polycaryophyllene could be easily modulated from -35 °C to a range between -25 and 10 °C by changing the type of cross-linking agent. The curing process led to the improvement of thermal stability ranging from 200 °C to around 340 °C. Finally, the network storage modulus varied from 1 to 100 MPa at room temperature.

show abstract

Dicumyl Peroxide Thermal Decomposition in Cumene: Development of a Kinetic Model

Cited by 25 publications

References 12 publications

Caryophyllene as a Precursor of Cross-Linked Materials

Caryophyllene as a Precursor of Cross-Linked Materials

Cure kinetics of a polysilazane system: Experimental characterization and numerical modelling

Caryophyllene as a Precursor of Cross-Linked Materials

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