Unusual activation by solvent of the ethylene free radical polymerization

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

1 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265

Ethylene polymerization is performed industrially either by radical polymerization under severe conditions (1000-4000 bar, 200-300°C) or by catalytic mechanism at lower temperatures (usually less than 100°C) and pressures (below 50 bar). Standard radical polymerization conditions are too severe to permit a fine control of the macromolecular architecture. Under milder conditions (100 bar, 70°C), radical ethylene polymerization is assumed ineffective which has been confirmed in bulk (supercritical ethylene). However, we have shown that the efficiency of this polymerization is strongly dependant of the solvent. This unusual activation by solvent has been rationalized using theoretical considerations. A second effect investigated is the influence of solvent on PE molecular weight. Indeed PE with either low molecular weight and high chain-end functionality or higher molecular weight can be synthesized according to the solvent used.

Mots clés: solvent effect; ethylene; EOS

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

Etienne Grau, Jean-Pierre Broyer, Christophe Boisson, Roger Spitz, Vincent Monteil. Unusual activation by solvent of the ethylene free radical polymerization. Polymer Chemistry, 2011, 2 (10), pp.2328--2333. ⟨10.1039/c1py00200g⟩. ⟨hal-01874380⟩