Particle growth of magnesium alkoxide as a carrier material for polypropylene polymerization catalyst
Images from scanning electron microscopy, transmission electron microscopy and X-ray diffraction profiles of typical magnesium diethoxide (MGE) particles obtained by the reaction of ethanol, metal magnesium and iodine showed the round MGE particle (tertiary particle) had a layer structure consisting of many crystalline fragments (secondary particles) comprising many minute crystals (primary particles). It was clearly shown that each precipitated secondary particle had not agglomerated, but had repeatedly grown and combined with others. From the investigation of the course of a reaction, it was suggested the MGE crystals grown on Mg metal exfoliated as “lump-like” seeds, and crystal growth on seeds proceeded such that the shapes of the final MGE particles were more spherical than those of their seeds. It was presumed from a model reaction that the enhancement of MGE solubility by I2 addition to form the quasi-stable complex nMg(OEt)2·MgI2·mEtOH was the key process in the formation of plate crystals. The relationship between the size of crystalline fragments and crystallization rate (reaction rate, MGE solubility) was discussed.The catalyst, when prepared using MGE as the carrier material, exhibited exceptionally high polymerization activity than when it was prepared with MgCl2 alcohol complex (MgCl2·ROH). We presume that this is because particles of the MGE-based catalyst are porous, and because the formation of active species of the supported Ti and monomer diffusion progressed adequately from the surface of the particle to its internal parts.
Graphical abstractThe synthesis reaction mechanism of magnesium diethoxide (MGE) was considered in detail. It was suggested that MGE particles had round shapes and the unique layer structure of three generation comprising plate crystals and these were grown through the increase in MGE solubility by the addition of I2, the exfoliation of crystalline seeds, and the change of precipitation rate of MGE.Figure optionsDownload full-size imageDownload as PowerPoint slide
Journal: Applied Catalysis A: General - Volume 350, Issue 2, 30 November 2008, Pages 197–206