AIChE Journal, Vol.52, No.5, 1866-1876, 2006
Hydrogen response in liquid propylene polymerization: Towards a generalized model
Liquid propylene batch experiments in the absence of a gas phase have been carried out using a highly-active MgCl2/TiCl4/phthalate/silane/AlR3 catalyst at varying temperatures (60-80 degrees C) and molar hydrogen-monomer ratios of 0-10 mmol/mol. With increasing hydrogen concentration the polymerization rate increases rapidly, reaching a constant value at concentrations above 1.4 mmol/mol; pseudo-first-order catalyst deactivation constant increases; molecular weight decreases; polydispersity decreases slightly; but average molecular weight and polydispersity increase with increasing temperature. Polymerization rate, deactivation constant, and average molecular weight can be modeled based on a consistent dormant site mechanism assuming an (averaged) quasi-single-site model. (c) 2006 American Institute of Chemical Engineers.
Keywords:liquid phase propylene polymerization;polymerization kinetics;dormant-site theory;molecular weight distribution;catalyst decay;hydrogen response