Astrategy for combining Ziegler–Natta andmetallocene catalysis to synthesize broad/bimodalmolecularweight-distribution
polypropylene (PP) is proposed. The chemistry is centered on a fabrication as well as utilization of a modified MgCl2/TiCl4 Ziegler–Natta catalyst with incorporated C2-symmetric ansametallocene catalyst capable of promoting isospecific propylene polymerization. A MgCl2/TiCl4 catalyst is prepared in the presence of a 1,3-diether internal electron donor, 9,9-bis(methoxymethyl)fluorene (BMMF), which, with a porous physical architecture, is able to accommodate MAO-encapsulated and protected rac-[methylene(3-tert-butyl-1-indenyl)2]ZrCl2 (rac-CH2(3-t-Bu-1-Ind)2ZrCl2) without impairing
its own composition and structure. Activation of the two-piece catalyst is found to be best conducted by pairing triisobutylaluminium(TIBA)insteadoftriethylaluminium(TEA) withMAO. Polymerizationofpropylene with TIBA-MAO-activated modified MgCl2/TiCl4 catalyst containing rac-CH2(3-t-Bu-1-Ind)2ZrCl2 produces broad/bimodalmolecular-weight-distributionPP withtunable compositions.Moreover, reactor particles of PP thus produced are ensured with good granular morphology, which is crucial for application in modern PP industry with dominant bulk and gas polymerization processes