Supercritical behavior in free radical polymerization of ethylene in the medium pressure range

Etienne Grau (1, 2) , Jean-Pierre Broyer (3) , Christophe Boisson (3) , Roger Spitz (3) , Vincent Monteil (3)

1 LCPO - Laboratoire de Chimie des Polymères Organiques
2 Team 2 LCPO : Biopolymers & Bio-sourced Polymers
3 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265

Free radical polymerization of ethylene in an intermediate pressure and temperature range (P(ethylene) < 250 bar and 50 degrees C < T < 90 degrees C) in the presence of an organic solvent has been studied. Under selected conditions ( P, T) and according to the amount of organic solvent added, either a supercritical monophasic or a biphasic medium is obtained. In the case of a biphasic medium, polymerization occurred in the liquid phase in which radical initiator and ethylenes are dissolved. The transition between a monophasic to a biphasic medium has been predicted using thermodynamic calculations and has been related to experimental observations such as the dependence of polymerization activity versus solvent volume.

Mots clés: Polyethylene; ethylene; solubility; EOS

Domaines: Polymères; Matériaux; Chimie théorique et/ou physique; Science des matériaux [cond-mat.mtrl-sci]

Etienne Grau, Jean-Pierre Broyer, Christophe Boisson, Roger Spitz, Vincent Monteil. Supercritical behavior in free radical polymerization of ethylene in the medium pressure range. Physical Chemistry Chemical Physics, 2010, 12 (37), pp.11665-11669. ⟨10.1039/c004447d⟩. ⟨hal-00948910⟩