Stereochemical composition-properties relationships in isotactic polypropylenes obtained with different catalyst systems

The influence of stereochemical composition of the radial growth rate of spherulites, the nucleation density, the overall rate of crystallization and the thermal behaviour of fractions of iPP samples synthesized with different catalyst systems (low, high and very high yield) was investigated. The study used ¹³C n.m.r., differential scanning calorimetry (d.s.c.) and optical microscopy. The ¹³C n.m.r. analysis showed that due to the presence of catalytic sites with different stereoregulating capability the catalyst system produces polypropylene with different stereoregularity. It was found that the growth rate of spherulites and the overall rate of crystallization are strictly related to the stereochemical structure of the polypropylene. Moreover, for the low yield iPP, phenomena of secondary crystallization were observed by Avrami analysis of the overall kinetics. Values of the equilibrium melting temperature (T_m), energy of nucleation (Δø1) and surface free energy of folding (σe) of iPP lamellar crystals have been determined according to the kinetic theory of polymer crystallization. The values of such thermodynamic quantities as well as the thermal behaviour of various iPP are strongly dependent upon the amount and distribution of configurational irregularities existing along the chains and upon the molecular mass distribution.