Distribution kinetics of radical mechanisms: Reversible polymer decomposition

Kodera, Yōichi; McCoy, Benjamin J.

doi:10.1002/aic.690431208

Cited by 109 publications

(194 citation statements)

References 30 publications

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“…7 Let P(x), R(x), and R e (x), represent the polymer, Scheme 2 Scheme 1 radical, and end radicals of molecular weight x. For the polymers studied, both the specific products occur at the same step, and thus Q s represents both the specific products.…”

Section: Kinetic Modelmentioning

confidence: 99%

Thermal degradation kinetics of para‐substituted poly (styrene peroxide)s in solution

Chattopadhyay

Madras

et al. 2002

J of Applied Polymer Sci

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ABSTRACT:The thermal degradation of three polymeric peroxides of styrene monomers with substituents in the para position was studied at various temperatures (65, 75, 85, and 95°C). A continuous distribution model was used to evaluate the rate coefficients for the random-chain and chain-end scission degradation from the evolution of molecular weight distributions with time. The activation energy determined from the temperature dependence of the rate coefficients was in the range 18 -22 kcal mol Ϫ1 . This result suggests that the thermal degradation of polyperoxide is controlled by the dissociation of the O-O bonds in the polymer backbone.

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Section: Kinetic Modelmentioning

confidence: 99%

Thermal degradation kinetics of para‐substituted poly (styrene peroxide)s in solution

Chattopadhyay

Madras

et al. 2002

J of Applied Polymer Sci

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“…16 however, and also provides an explanation for the activation energies observed for random scission and chain-end scission (Kodera and McCoy, 1997).…”

Section: Case 1 Reversible Random Chain Scissionmentioning

confidence: 99%

“…The population balance equations for p(x,t) and for radical MWD, r(x,t), are as follows (Kodera et al, 1997):…”

Section: Case 1 Reversible Random Chain Scissionmentioning

confidence: 99%

Fundamental Kinetics of Supercritical Coal Liquefaction: Effect of Catalysts and Hydrogen-Donor Solvents

McCoy¹,

Madras²,

Smith³

et al. 1997

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“…Applying the moment generation function to a PBE yields the n-th moment of the MWD 20) . Typical moment expressions derived from rate expressions are summarized in Table 1 9), 19) . For example, applying the moment operation to Eq.…”

Section: Moment Solutionsmentioning

confidence: 99%

“…Oligomer formation via the back-biting reaction is known in polymer chemistry, and corresponds to the Rice _ Kossiakoff mechanism 26) in hydrocarbon cracking. We introduce such radical mechanisms into distribution kinetics in order to construct kinetic models of polymers and their products 19) . Typical radical reactions are chosen as major elementary reactions to describe the fate of a polymer upon pyrolysis.…”

Section: Typical Radical Reactions In Polymer Decompositionmentioning

confidence: 99%

Distribution Kinetics of Plastics Decomposition

Kodera

McCoy

2003

J. Jpn. Petrol. Inst.

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Distribution kinetics is a method to analyze polymer reactions kinetically in terms of the molecular-weight (or chain-length) distributions (MWDs) of components in a macromolecular mixture. Governing equations for temporal and spatial dependence of the MWDs are based on population balance equations (PBEs) for the distinguishable species. Moments of the MWDs are related to observable properties, such as average MW and polydispersity, and can be measured for polymeric systems by procedures such as size-exclusion chromatography. The moments are related mathematically to rate parameters in the PBEs. The distribution kinetics approach is thus a method for interpreting experimental observations of MWD dynamics in terms of chemical reaction mechanisms.

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Distribution kinetics of radical mechanisms: Reversible polymer decomposition

Cited by 109 publications

References 30 publications

Thermal degradation kinetics of para‐substituted poly (styrene peroxide)s in solution

Thermal degradation kinetics of para‐substituted poly (styrene peroxide)s in solution

Fundamental Kinetics of Supercritical Coal Liquefaction: Effect of Catalysts and Hydrogen-Donor Solvents

Distribution Kinetics of Plastics Decomposition

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