Isotactic polypropylene/ethylene-co-propylene blends: Influence of the copolymer microstructure on rheology, morphology, and properties of injection-molded samples

Abstract

Meltrheological behavior, phase morphology, and impact properties of isotactic-polypropylene (iPP)-based blends containing ethylene–propylene copolymer (EPR) synthesized by means of a titanium-based catalyst with very high stereospecific activity (EPRTi) were compared to those of iPP/EPR blends containing EPR copolymers synthesized by using a traditional vanadium-based catalyst (EPRV). The samples of EPR copolymers were synthesized ad hoc. They were characterized by comparable propylene content, average molecular masses, and molecular mass distribution in order to assess the effects of distribution of composition and sequence lengths of the structural units on the structure–properties correlations established in the melt and in the solid state while studying different iPP/EPR pairs.1–5 Differential scanning calorimetry, (DSC), wide-angle X-ray spectroscopy (WAXS), small-angle X-ray (SAXS), and scanning electron microscopy (SEM) investigations showed that the EPRTi chain is characterized by the presence of long ethylenic sequences with constitutional and configurational regularity required for crystallization of the polyethylene (PE) phase occurring, whereas a microstructure typical of a random ethylene–propylene copolymer was exhibited by the EPRV copolymer. The different intra- and intermolecular homogeneity shown by such EPR phases was found to affect their melt rheological behavior at the temperatures of 200 and 250°C; all the EPRTi dynamic–viscoelastic properties resulting were lower than that shown by the EPRV copolymer. As far as the melt rheological behavior of the iPP/EPRV and iPP/EPRTi blends was concerned, both the iPP/EPR pairs are to be classified as “negative deviation blends” with G′ and G" values higher than that shown by the plain components. The extent of the observed deviation in the viscosity values and of the increase in the amounts of stored and dissipated energy shown by such iPP/EPR pairs was found to be dependent on copolymer microstructure, being larger for the melts containing the EPRTi copolymer. The application of the Cross–Bueche equation also confirmed that, in absence of shear, the melt phase viscosity ratio is the main factor in determining the viscosity of iPP/EPR blends and their viscoelastic parameters. The general correlation established between EPR dispersion degree (range of particle size and number-average particle size), as determined in injection-molded samples, and melt phase viscosity ratio (μ) was ratified; the type of dependence of EPR size upon μ value was in qualitative agreement with the prediction of the Taylor–Tomotika theory. Contrary to expectation,1–5 for test temperature close to iPP Tg, EPRV particles ranging in size between 0.75 and 1.25 μm resulted and were more effective than EPRTi particles, ranging in size between 0.25 and 0.75 μm, in promoting multiple craze formation. Also taking into account the SAXS results, revealed that the molecular superstructure (i.e., crystalline lamellar thickness and amorphous interlayer) of the iPP matrix is unaffected by both the presence of EPRTi and EPRV phase. The above finding was related to the ethylenic crystallinity degree shown by the EPRTi copolymer. In particular, such a degree of crystallinity was supposed to deteriorate toughening by decreasing the tie molecules density in the EPRTi domains, notwithstanding the beneficial effect of the ethylenic lamellar buildup. For test temperature close to room temperature, the ductile behavior exhibited by the iPP/EPRTi blends was accounted for by a predominant shear yielding fracture mechanism probably promoted by a high concentration of interlamellar tie molecules among iPP crystallites in agreement with DSC results. Nonisothermal crystallization experiments showed, in fact, that the crystallization peak of the iPP phase from iPP/EPRTi melt is shifted to higher temperatures noticeably, thus indicating a material characterized by a comparatively higher number of spherulites per unit value grown at lower apparent undercooling values. Accordingly, WAXS analysis revealed comparatively higher iPP crystal growth in the directions perpendicular to the crystallographic planes (110) and (040) of the iPP. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 701–719, 1999