Diffusion-Controlled Free Radical Polymerization. Effect on Polymerization Rate and Molecular Properties of Polyvinyl Chloride

Hamielec, A. E.; Gomez-vaillard, R.; Marten, F. L.

doi:10.1080/00222338208056498

Cited by 34 publications

(11 citation statements)

References 12 publications

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“…The free-radical VCM suspension polymerization mechanism includes the following elementary reactions (Hamielec et al, 1982;Sidiropoulou and Kiparissides, 1990;Xie et al, 1991b):…”

Section: Reaction Kinetics and Molecular Property Equationsmentioning

confidence: 99%

“…Therefore, there is a strong incentive to develop comprehensive mathematical models capable of predicting the reactor behavior as well as the development of molecular properties during the course of polymerization. In the past several mathematical models have been developed to describe the two-phase suspension polymerization of VCM (Abdel-Alim and Hamielec, 1972;Kuchanov and Bort, 1973;Ray et al, 1975;Ugelstad et al, 1981;Chan et al, 1982;Hamielec et al, 1982;Kelsall and Maitland, 1983;Weickert et al, 1987aWeickert et al, ,b, 1988aXie et al, 1991b-d;Bretelle and Machietto, 1994;Dimian et al, 1995;Lewin, 1996). These have been recently reviewed by Sidiropoulou and Kiparissides (1990) and Yuan et al (1991).…”

Section: Introductionmentioning

confidence: 99%

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Dynamic Simulation of Industrial Poly(vinyl chloride) Batch Suspension Polymerization Reactors

Kiparissides

Daskalakis

Achilias

et al. 1997

Ind. Eng. Chem. Res.

142

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In the present study a comprehensive mathematical model is developed to simulate the dynamic behavior of industrial poly(vinyl chloride) (PVC) batch suspension polymerization reactors. More specifically, the model predicts the monomer concentration in the gas, aqueous, and polymer phases, the overall monomer conversion, the polymerization rate and polymer chain structural characteristics (e.g., number- and weight-average molecular weights, long-chain branching, short-chain branching, and number of terminal double bonds), the reactor temperature and pressure, and the jacket inlet and outlet temperatures over the whole polymerization cycle. An experimental reactor is employed to verify the theoretical model predictions. It is shown that experimental results on the time evolution of reactor temperature and pressure, the jacket inlet and outlet temperature, and the final conversion and molecular weight averages are in very good agreement with model predictions. The predictive capabilities of the model are also demonstrated through the simulation of experimental data recently reported in the literature. Finally some results on the optimization of the PVC production are presented.

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“…The free-radical VCM suspension polymerization mechanism includes the following elementary reactions (Hamielec et al, 1982;Sidiropoulou and Kiparissides, 1990;Xie et al, 1991b):…”

Section: Reaction Kinetics and Molecular Property Equationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dynamic Simulation of Industrial Poly(vinyl chloride) Batch Suspension Polymerization Reactors

Kiparissides

Daskalakis

Achilias

et al. 1997

Ind. Eng. Chem. Res.

142

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show abstract

“…In the most conventional kinetic scheme of FRP, chain‐end radicals only are accounted for and such species take part to reactions like initiation, propagation, and termination; in the specific case of PVC, the most relevant termination mechanism is chain transfer to monomer 36–40. Since this work is mainly focused on MCRs, the kinetic scheme has been updated to include a selection of the most relevant reactions involving this type of radicals: such selection has been based on literature evidences as well as on our own computational results discussed above.…”

Section: Kinetic Modelmentioning

confidence: 99%

Quantum Chemical Investigation of Secondary Reactions in Poly(vinyl chloride) Free‐Radical Polymerization

Cuccato¹,

Dossi²,

Moscatelli³

et al. 2012

Macro Reaction Engineering

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Free-radical polymerization of vinyl chloride is investigated computationally with special attention to the secondary reactions involving mid-chain radicals (MCRs). Namely, the rate constants of backbiting, chain scission, chain transfer, and propagation reactions are evaluated using a density functional theory method. The rate coefficients of such reactions are estimated taking into account the position of the radical along the chain as well as its distance from the chain-end. In particular 1:5, 5:1, and 5:9 backbiting are the most relevant secondary reactions, followed by the slower propagation of MCRs. Finally, a kinetic model of suspension polymerization including the investigated reactions is developed, in order to determine their impact on the quality of the final polymer.

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“…If molecular weight is mainly controlled by transfer reactions (only a small amount of polymer is produced by termination), the molecular weight and branching development can be calculated as follows: 2,3 where: X monomer conversion, number-average of branch points per polymer molecule, n k fm transfer-to-monomer rate constant, k p propagation rate constant, k fp transfer rate constant, number-average molecular weight of polymer, weight average molecular weight of polymer, V F transfer rate, number of long branches per 1000 monomer units, M R molecular weight of the repeat unit, B m , B p , V FcrM , V Fcrp parameters which can be found by fitting the rate and the molecular weight data. 93 …”

mentioning

confidence: 99%

PVC Morphology

Wypych¹

2015

PVC Degradation and Stabilization

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Diffusion-Controlled Free Radical Polymerization. Effect on Polymerization Rate and Molecular Properties of Polyvinyl Chloride

Cited by 34 publications

References 12 publications

Dynamic Simulation of Industrial Poly(vinyl chloride) Batch Suspension Polymerization Reactors

Dynamic Simulation of Industrial Poly(vinyl chloride) Batch Suspension Polymerization Reactors

Quantum Chemical Investigation of Secondary Reactions in Poly(vinyl chloride) Free‐Radical Polymerization

PVC Morphology

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