Influence of various pretreatments on molecular and rheological properties of a linear and a long-chain branched polypropylene

The influence of a mechanical or a thermal pretreatment of a linear (L-PP) and a long-chain branched polypropylene (LCB-PP) in the molten state was studied. The molar mass distributions and the branching structure were determined by high-temperature gel permeation chromatography HT-GPC coupled with laser-light scattering. The samples were extruded through long or short capillaries of various geometries corresponding to a predominant shear or elongational deformation. As a rheological probe, the extrudate swell at low stresses was measured for the differently pretreated samples. For the L-PP, neither molecular nor rheological changes were observed. However, the extrudate swell of the LCB-PP was found to decrease with increasing volume throughput. It was more strongly affected by shear in the capillary than by molecule stretching in the entry region. The smaller extrudate swell was accompanied by a decrease of the high molar mass tail of the LCB-PP, which could be the reason for the decay of swell, in principle. However, a comparable degradation of the high molar mass tail was obtained by a pure thermal treatment that was shown to leave the extrudate swell unchanged. This result and the unaffected branching structures found by high-temperature gel permeation chromatography (HT-GPC) support the hypothesis of a change of the branching topography by the mechanical pretreatment.