Lanthanide metal-organic frameworks as ziegler–natta catalysts for the selective polymerization of isoprene

Vitorino, Marta J., Devic, Thomas, Tromp, Moniek, Férey, Gérard and Visseaux, Marc (2009) Lanthanide metal-organic frameworks as ziegler–natta catalysts for the selective polymerization of isoprene. Macromolecular Chemistry and Physics, 210, 1923-1932. (doi:10.1002/macp.200900354).

Abstract

The unprecedented ability of neodymium-based metal organic frameworks (MOFs) as
polymerisation pre-catalysts towards isoprene is reported. Combined with methylaluminoxane
(MAO) or modified MAO (MMAO), they afford mainly cis-selective polyisoprene, up to
90.7%. Both the activity and the selectivity are tentatively ascribed to the intrinsic microstructure
of the starting materials. Compared to conventional carboxylates, MOFs associated
to an Al co-catalyst are less active but the selectivity is found to be higher, and it
may be modified by controlling the access to the pores, which would be favored at higher
temperatures. Some residual crystalline
MOF remains disseminated within the
polymer matrix, as shown by X-ray
diffraction and X-ray absorption spectroscopy
studies.

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