An analysis of the elastic properties of syndiotactic polypropylene at different temperatures
is reported. Fibers stretched at low temperatures are in the trans-planar form III, which transforms into
the helical form II upon the release of the tension, whereas fibers stretched at high temperatures are in
the stable helical form I. The mechanical analysis of these fibers has shown that only at room temperatures
the specimens show good elastic properties. The elastic recovery of the samples is in part lost also at
room temperature in annealed fibers, which are in the stable form I, in both the stretched and unstrained
states. When the structural transition from the trans-planar form III into the helical form occurs upon
removing the tension, a nearly total elastic recovery is observed. Only a partial elastic recovery is instead
observed when this transition is absent. The relative amount of crystalline phase in unoriented films
and in stretched and stress-relaxed fibers is rather constant (≈40−43%) and does not depend on the
stretching temperature in the range 25−80 °C. These data indicate that the elastic behavior of syndiotactic
polypropylene is in part linked to the enthalpy gain achieved when the tension is removed, due to the
metastability, in the unstrained state, of the trans-planar form, which transforms into the stable helical
form. On the other hand, also an entropic factor must play a role, due to the entangled amorphous chains
which experience a reversible conformational transition between the disordered (coil) and extended
conformations during the stretching and relaxing process.
Allylic complexes of lanthanides bearing a fluorenyl-based ligand are active single-component catalysts for the polymerization of styrene, giving highly syndiotactic polymers (rrrr > 99%) with low to high molecular weight (Mn = 8000-135 000) and narrow polydispersities (Mw/Mn = 1.25-2.1).
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