Comparing End-of-Life Vehicle (ELV) and Packaging-Based Recyclates as Components in Polypropylene-Based Compounds for Automotive Applications.

Increasing recycled plastic content in cars to 25% by 2030 is one of the key measures for decarbonizing the automotive industry defined by the European Commission. This should include the recovery of plastics from end-of-life vehicles (ELVs), but such materials are hardly used in compounds today. To close the knowledge gap, two ELV recyclate grades largely based on bumper recycling were analyzed in comparison to a packaging-based post-consumer recyclate (PCR). The composition data were used to design polypropylene (PP) compounds for automotive applications with virgin base material and mineral reinforcement, which were characterized in relation to a commercial virgin-based compound. A compound with a 40 wt.-% ELV-based bumper recyclate can exceed one with just a 25 wt.-% packaging-based recyclate in terms of stiffness/impact balance. While the virgin reference can nearly be matched regarding mechanics, the flowability is not reached by any of the PCR compounds, making further development work necessary.

Polyolefin Blends with Selectively Crosslinked Disperse Phase Based on Silane-Modified Polyethylene.

Polypropylene-based multiphase compositions with a disperse elastomer phase provide superior impact strength. Making this property indifferent to processing steps requires stabilization of the morphology of these materials. Various approaches have been tested over time, each of which shows limitations in terms of performance or applicability. Using polyethylene (PE) homo- and copolymers capable of silane-based crosslinking as modifiers was explored in the present study, which allows decoupling of the mixing and crosslinking processes. Commercial silane-copolymerized low-density PE (LD-PEX) from a high-pressure process and silane-grafted high-density PE (HD-PEX) were studied as impact modifiers for different types of PP copolymers, including non-modified reference PE grades, LDPE and HDPE. Blends based on ethylene-propylene random copolymers (PPR) and based on impact- (PPI) and random-impact (PPRI) copolymers show improvements of the stiffness-impact balance; however, to different degrees. While the absolute softest and most ductile compositions are achieved with the already soft PPRI copolymer base, the strongest relative effects are found for the PPR based blends. Modifiers with lower density are clearly superior in the toughening effect, with the LD-PEX including acrylate as second comonomer sticking out due to its glass transition around -40 °C. The impact strength improvement found in most compositions (except at very high content) results, however, not from the expected phase stabilization. For comparable systems, particle sizes are normally higher with crosslinking, probably because the process already starts during mixing. Thermoplastic processability could be retained in all cases, but the drop in melt flow rate limits the practical applicability of such systems.

Prospects for Recyclable Multilayer Packaging: A Case Study.

Food preservation is an essential application for polymers, particularly in packaging. Complex multilayer films, such as those used for modified atmosphere packaging (MAP), extend the shelf life of sensitive foods. These mostly contain various polymers to achieve the necessary combination of mechanic, optic, and barrier properties that limit their recyclability. As the European Union's Circular Economy Action Plan calls for sustainable products and business models, including waste prevention policies and recycling quotas, with plastic packaging being a high priority, solutions towards more sustainable multilayer packaging are urgently needed. This study evaluated and compared the recycling potential of functionally equivalent PET (polyethylene terephthalate) and PP (polypropylene) post-consumer MAP through structure analysis and recycling simulation. The structure analysis revealed that both types of MAP contained functional (stability) and barrier layers (oxygen and moisture). The recycling simulation showed that the PP-based packaging was recyclable 10 times, maintaining its mechanical properties and functionality. At the same time, the PET-based MAP resulted in a highly brittle material that was unsuitable for reprocessing into similar economic value products. The secondary material from the PP-based MAP was successfully manufactured into films, demonstrating the functional possibility of closed-loop recycling. The transition from a linear to a circular economy for MAP is currently still limited by safety concerns due to a lack of sufficient and efficient purification methods, but the proper design of multilayers for recyclability is a first step towards circularity.

Polymerization in the Borstar Polypropylene Hybrid Process: Combining Technology and Catalyst for Optimized Product Performance.

Producing isotactic polypropylene (iPP) homo- and copolymers in a wide composition and property range according to customer demand requires perfect alignment between the process technology, catalyst system and polymer structure. The present review shows this for the Borstar® PP process, a hybrid process employing liquid bulk and gas phase stages, in an exemplary way. It starts with the process design and continues through two generations of Ziegler-Natta catalyst development history to the design of advanced multimodal random and multiphase copolymers. Essential elements of each of the three areas contributing to performance range are highlighted, and an outlook to future development is given.

Crystallization of Random Metallocene-Catalyzed Propylene-Based Copolymers with Ethylene and 1-Hexene on Rapid Cooling.

Propylene-based random copolymers with either ethylene or 1-hexene as comonomer, produced using a metallocene catalyst, were studied regarding their crystallization behaviors, with a focus on rapid cooling. To get an impression of processing effects, fast scanning chip calorimetry (FSC) was used in addition to the characterization of the mechanical performance. When comparing the comonomer type and the relation to commercial grades based on Ziegler-Natta-type catalysts, both an interaction with the catalyst-related regio-defects and a significant difference between ethylene and 1-hexene was observed. A soluble-type nucleating agent was found to modify the behavior, but to an increasingly lesser degree at high cooling rates.

Gelation and Crystallization Phenomena in Polyethylene Plastomers Modified with Waxes.

Polyethylene (PE) plastomers, single-site catalyst-based homogeneous linear low-density PEs (LLDPEs), combine low crystallinity, softness, and elasticity, making them ideal candidates for numerous applications such as hot-melt adhesives (HMA). As plastomers crystallize rather slowly, a number of possible low molecular weight polyolefin components were tested to accelerate solidification. An ideal modifier should accelerate solidification while maintaining transparency and softness of the base polymer. A Queo plastomer type was modified with different PE and PP waxes at concentrations of 5 to 25 wt.-%. Next to conventional calorimetry, a rheological technique was applied to study solidification. The resulting morphology was studied by atomic force microscopy, and the final compositions were investigated regarding their mechanical and optical performance. Accelerated solidification was observed in all cases, but a quite different course of structure formation could be concluded. PE waxes dissolve in the melt state, forming a lamellar network during cooling, whereas PP waxes form a heterogeneous blend in the melt for which the wax droplets solidify before the matrix. The particulate-type modification by the PP wax also affects stiffness less while retaining transparency better.

New Insights into Crystallization of Heterophasic Isotactic Polypropylene by Fast Scanning Chip Calorimetry.

The crystallization kinetics of metallocene-catalyzed heterophasic isotactic polypropylene composed of a matrix of isotactic polypropylene (iPP) and rubbery particles made of random ethylene-propylene copolymers (EPC), often denoted as heterophasic iPP copolymers, was analyzed as a function of the cooling rate and supercooling in nonisothermal and isothermal crystallization experiments, respectively. Fast scanning chip calorimetry (FSC) allowed assessing crystallization at processing-relevant conditions, and variation of the content (0-39 wt %) and composition (0-35 wt % propylene counits) of the EPC particles revealed qualitatively new insight about mechanisms of heterogeneous crystal nucleation. For neat iPP homopolymer, the characteristic bimodal temperature dependence of the crystallization rate due to predominance of heterogeneous and homogeneous crystal nucleation at high and low temperatures, respectively, is reconfirmed. At high temperatures, in heterophasic iPP, the here studied ethylene-(C2)-rich EPC particles accelerate crystallization of the iPP-matrix, with the acceleration or nucleation efficacy correlating with the EPC-particle content. The crystallization time reduces by more than half in presence of 39 wt % EPC particles. An additional nucleating effect of the EPC particles on iPP-matrix crystallization is detected after their crystallization, suggesting that liquid/rubbery particles are less effective than solid/semicrystalline particles in affecting crystallization of the surrounding iPP-matrix. At low temperature, homogeneous crystal nucleation in the iPP-matrix outpaces all heterogeneous nucleation effects, and the matrix-crystallization rate is independent of the sample composition. The obtained results lead to the conclusion that the crystallization kinetics of iPP can be affected significantly by the content and composition of EPC particles, even towards superfast crystallizing iPP grades.

Systematic Investigation on the Structure-Property Relationship in Isotactic Polypropylene Films Processed via Cast Film Extrusion.

The effect of cast film extrusion processing conditions, such as the chill-roll temperature, temperature of the melt, and line speed, on the structure of different isotactic polypropylene homo- and random copolymers has been investigated by means of Small- and Wide-Angle X-ray Scattering (SAXS and WAXS) and correlated to stiffness and haze. Stiffness and transparency have been found to be strongly dependent on the temperature of the chill-roll. Interestingly, line speed has been found to affect the total crystallinity when the chill-roll temperature is increased, while an overall minor effect of the melt temperature was found for all cast films. The polymer characteristics, defined by the catalyst nature and comonomer content, affect the final material performance, with the single-site catalyzed grades performing better in both mechanics and optics. Haze levels were found to correlate with the mesophase content rather than to α-crystallinity and to be dependent on the domain size for all grades. The remarkably low haze levels reached by the single-site grade with higher isotacticity can arise from high nucleation rate and orientational effects, which ultimately yield smaller and smoother scattering domains.

Effect of the molecular structure of the polymer and nucleation on the optical properties of polypropylene homo- and copolymers.

Two soluble nucleating agents were used to modify the optical properties of nine PP homo- and random copolymers. The ethylene content of the polymers changed between 0 and 5.3 wt %. Chain regularity was characterized by the stepwise isothermal segregation technique (SIST), while optical properties by the measurement of the haze of injection molded samples. Crystallization and melting characteristics were determined by differential scanning calorimetry (DSC). The analysis of the results proved that lamella thickness and change in crystallinity influence haze only slightly. A model was introduced which describes quantitatively the dependence of nucleation efficiency and haze on the concentration of the nucleating agent. The model assumes that the same factors influence the peak temperature of crystallization and optical properties. The analysis of the results proved that the assumption is valid under the same crystallization conditions. The parameters of the model depend on the molecular architecture of the polymer. Chain regularity determines supermolecular structure and thus the dependence of optical properties on nucleation.