Summary: Propylene was polymerized by three homogenous metallocene catalytic systems: rac-Me 2 Si (Ind) 2 ZrCl 2 (CAT-1), rac-Et(Ind) 2 ZrCl 2 (CAT-2) and rac-Me 2 Si(2-Mebenzoind) 2 ZrCl 22 ZrCl 2 (CAT-3) at 50 8C. In function of the molecular-average weight results of poly(propylene)s obtained, rac-Et(Ind) 2 ZrCl 2 (CAT-2) and rac-Me 2 Si(2-Mebenzoind) 2 ZrCl 2 (CAT-3) were combined in different proportions (wt %/wt %) of (CAT-2/CAT-3) for obtaining a new poly(propylene) with a bimodal molecular weight distribution consisting in clearly separated low and high molecular weight polymer fractions with a difference between them of an order of magnitude. The polymers obtained were compared with those coming from melt mixing of two poly(propylene)s with different molecular weights in an extruder. Both methods allow obtaining bimodal poly(propylene)s, but polymer melt blending shows partial miscibility effects and less crystallinity while binary catalytic systems have several advantages such as lower costs and easier to process that can be controlled to tailor properties together with intimate mixing of high and low molecular weight components.

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The complex polymorphic behaviour of four syndiotactic polypropylene (sPP) samples have been analysed by means of DSC and WAXD techniques. Two samples (sPP1, sPP2) were synthesised via metallocene polymerization by using the ansa-zirconocene Ph2C(Cp)(9-Flu)ZrCl2 as catalyst. Finally, two additional specimens with different molar masses (sPP1-Fr1, sPP1-Fr2) were prepared from the most syndiotactic sPP1 sample by temperature gradient extraction. The WAXD analysis shows that together with the orthorhombic form I, form II can coexist in a variable but small proportion depending on both the chain features and the processing conditions. The relative contribution of the disordered and the ordered types of form I is also dictated by molar mass, configurational microstructure as well as processing conditions. The observed changes in the thermal properties as measured by DSC and in the mechanic-dynamical relaxations of the samples, on slowing the crystallisation rate down, can be rationalised in terms of two concurrent processes, namely the perfection undergone by the crystals and the segregation of the amorphous phase.