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Updated: Jun 10, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
Supercritical behavior in free radical polymerization of ethylene in the medium pressure range
Etienne Grau1, Jean-Pierre Broyer, Christophe Boisson
1Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS, UMR 5265 Laboratoire de Chime Catalyse Polymères et Procédés (C2P2), LCPP Team, Bat 308F, 43 Bd du 11 novembre 1918, F-69616 Villeurbanne, France. grau@lcpp.cpe.fr
Abstract:
Free radical polymerization of ethylene in an intermediate pressure and temperature range (P(ethylene) < 250 bar and 50 °C < T < 90 °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.
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