Structure–Property Relationship in Isotactic Polypropylene Under Contrasting Processing Conditions

Polypropylene (PP), with its good physical, thermal, and mechanical properties and excellent processing capabilities, has become one of the most used synthetic polymers. It is known that the overall properties of semicrystalline polymers, including PP, are governed by morphology, which is influenced by the crystallization behavior of the polymer under specific conditions. The most important industrial PP remains the isotactic one, and it has been studied extensively for its polymorphic characteristics and crystallization behavior for over half a century. Due to its regular chain structure, isotactic polypropylene (iPP) belongs to the group of polymers with a high tendency for crystallization. The rapid quenching of molten iPP fails to produce a completely amorphous polymer but leads to an intermediate crystalline order. On the other hand, slow cooling yields a material with high crystalline content. The processing conditions that occur in practice and industry are between these two extremes and, in some cases, are even very close. Therefore, the study of limits in processability and the impact of extreme preparation conditions on morphology, structure, thermal, and mechanical properties fills a gap in the current understanding of how the processing conditions of iPP can be used to design the desired properties for specific applications and is in the focus of this research. The first set of samples (Q samples) was obtained by rapid quenching, while the second was prepared by very slow cooling from the melt to room temperature (SC samples). Testing of samples was performed by optical microscopy (OM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic dielectric spectroscopy (DDS), and mechanical measurements. Characterization revealed that slowly cooled samples exhibited a significantly higher degree of crystallinity and larger crystallites (χ ≥ 55% and L(110) ≈ 20 nm), compared to quenched samples (χ < 30%, L(110) ≤ 3 nm). Mechanical testing showed a drastic contrast: quenched samples exhibited elongation at break > 500%, while slowly cooled samples broke below 15%, reflecting their brittle behavior. For the first time, DDS is applied to investigate molecular mobility differences between processing-dependent structural forms, specifically the mesomorphic (smectic) and α-monoclinic forms. In slowly cooled samples, α relaxation exhibited both enhanced intensity and an upward temperature shift, indicating stronger structural constraints due to a much higher crystalline phase content and significantly larger crystallite size, respectively. These findings provide novel insights into the structure–property–processing relationship, which is crucial for industrial applications.