Long-chain branching (LCB) is known as a suitable method to increase the melt strength behavior of linear polypropylene (PP), which is a fundamental weakness of this material. This enables the modification of various properties of PP, which can then be used—in the case of PP recyclates—as a practical “upcycling” method. In this study, the effect of five different peroxides and their effectiveness in building LCB as well as the obtained mechanical properties were studied. A single screw extruder at different temperatures (180 and 240 °C) was used, and long-chain branched polypropylene (PP-LCB) was prepared via reactive extrusion by directly mixing the peroxides. The peroxides used were dimyristyl peroxydicarbonate (PODIC C126), tert-butylperoxy isopropylcarbonate (BIC), tert-Butylperoxy 2-ethylhexyl carbonate (BEC), tert-amylperoxy 2-ethylhexylcarbonate (AEC), and dilauroyl peroxide (LP), all with a concentration of 20 mmol/kg. The influence of the temperature on the competitive prevalent reactions of degradation and branching was documented via melt mass-flow rate (MFR), rheology measurements, and gel permeation chromatography (GPC). However, via extensional rheology, strain hardening could be observed in all cases and the mechanical properties could be maintained or even improved. Particularly, PODIC C126 and LP signaled a promising possibility for LCB in this study.

Blends of two long-chain branched polypropylenes (LCB-PP) and five linear polypropylenes (L-PP) were prepared in a single screw extruder at 240 °C. The two LCB-PPs were self-created via reactive extrusion at 180 °C by using dimyristyl peroxydicarbonate (PODIC C126) and dilauroyl peroxide (LP) as peroxides. For blending two virgin and three recycled PPs like coffee caps, yoghurt cups and buckets with different melt flow rate (MFR) values were used. The influence of using blends was assessed by investigating the rheological (dynamic and extensional rheology) and mechanical properties (tensile test and impact tensile test). The dynamic rheology indicated that the molecular weight as well as the molecular weight distribution could be increased or broadened. Also the melt strength behavior could be improved by using the two peroxide modified LCB-PP blends on the basis of PODIC C126 or PEROXAN LP (dilauroyl peroxide). In addition, the mechanical properties were consistently enhanced or at least kept constant compared to the original material. In particular, the impact tensile strength but also the elongation at break could be increased considerably. This study showed that the blending of LCB-PP can increase the investigated properties and represents a promising option, especially when using recycled PP, which demonstrates a real “up-cycling” process.

Long-chain branching (LCB) with peroxydicarbonates (PODIC) is known as a suitable post-reactor process to introduce strain-hardening behaviour and an increase of melt strength to a linear polypropylene (PP). This opens up new possibilities for processing and therefore application. Especially in the case of adding value to PP post-consumer waste, LCB is a promising approach. LCB takes place by a combination of chain scission and recombination after radical activation of the PP macromolecule. However, chemical modification of post-consumer waste is challenging because of the inhomogeneous composition and the manifold number of PP grades. The influence of the molar mass of the linear PP precursor on this reaction was studied with different PP grades ranging from extrusion grade to injection moulding grade. To exclude side effects, all PP grades had similar polydispersity indices. A PP with higher molar mass undergoes significant chain scission during the LCB process compared to a PP with low molar mass for injection moulding. Therefore, the two grades differ significantly in their branching number, which influences their behaviour in elongational flow.