Nitroxide‐Mediated Controlled Radical Styrene Polymerization Via a Mass‐Suspension Process

Abstract

Well controlled nitroxide‐mediated polymerizations of styrene using TEMPO as controller for the production of high molecular weight (MW) polystyrene have been run in a mass‐suspension process at the bench scale using molar ratios of nitroxide (N) to initiator (I) as low as N/I = 0.9. Previously, a kinetic study has been run in bulk polymerization in vials. The two processes show very similar results which demonstrates that the kinetic data collected in bulk can be used to scale‐up the mass‐suspension process. A mathematical model which can emulate the kinetic behavior of both processes has been built. Its kinetic parameters have been mostly taken from the literature and subjected to minimal data fitting using bulk reaction data. Some differences in the outputs of the two processes, especially at low conversions, are explained by the model and ascribed to temperature differences in the two processes.

Perspective on the controlled polymer‐modification of chitosan and cellulose nanocrystals: Towards the design of functional materials

“…[10,18] NMP can be carried out in solution or in bulk and has been successfully applied in various processes such as emulsion, miniemulsion, and suspension polymerization. [19][20][21] NMP can effectively polymerize styrenics or acrylates. Methacrylates can also be successfully polymerized if a controlling comonomer such as styrene or acrylonitrile is added to the system (~8-10 mol.%).…”

Anaerobic mono-digestion of wastewater from the main slaughterhouse in Yamoussoukro (Côte d’Ivoire): Evaluation of biogas potential and removal of organic pollution

“…[10,18] NMP can be carried out in solution or in bulk and has been successfully applied in various processes such as emulsion, miniemulsion, and suspension polymerization. [19][20][21] NMP can effectively polymerize styrenics or acrylates. Methacrylates can also be successfully polymerized if a controlling comonomer such as styrene or acrylonitrile is added to the system (~8-10 mol%).…”

Deterministic Approaches for Simulation of Nitroxide-Mediated Radical Polymerization

“…García-Leal et al [119] studied the NMP of styrene using TEMPO for the production of high molecular weight polystyrene in a mass-suspension process. The main characteristic of the mass-suspension polymerization is that a bulk prepolymerization is first carried out, followed by the suspension of the prepolymer at intermediate conversion in a continuous phase until total conversion.…”

“…The main characteristic of the mass-suspension polymerization is that a bulk prepolymerization is first carried out, followed by the suspension of the prepolymer at intermediate conversion in a continuous phase until total conversion. This reduces the inter-and intraparticle mass transfer that occurs at low to moderate conversion in a classic suspension polymerization and permits a better control of the particle size distribution [119]. The authors assumed that the system kinetics behaved as in a conventional polymerization and used the classical PBEs of NMP processed by the method of moments to predict average molecular properties and conversion.…”