Block copolymer micelles as nanoreactors for single-site polymerization catalysts

International audienceNew micelle-like organic supports for single site catalysts based on the self-assembly of polystyrene-b-poly(4-vinylbenzoic acid) block copolymers have been designed. These block copolymers were synthesized by sequential atom transfer radical polymerization (ATRP) of styrene and methyl 4-vinylbenzoate, followed by hydrolysis. As evidenced by dynamic light scattering, self-assembly in toluene that is a selective solvent of polystyrene, induced the formation of micelle-like nanoparticles composed of a poly(4-vinylbenzoic acid) core and a polystyrene corona. Further addition of trimethylaluminium (TMA) afforded in situ MAO-like species by diffusion of TMA into the core of the micelles and its subsequent reaction with the benzoic acid groups. Such reactive micelles then served as nanoreactors, MAO-like species being efficient activators of 2,6-bis[1-{(2,6-diisopropylphenyl)imino}ethyl]pyridinyl iron toward ethylene polymerization. These new micelle-like organic supports enabled the production of polyethylene beads with a spherical morphology and a high bulk density through homogeneous-like catalysis