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The unprecedented growth and socioeconomic impacts of polyolefins clearly outline a major success story in the world of polymer science. Polyolefins revolutionizes industries such as health care, construction, and food packaging. Despite the benefits of polyolefins, there is a rising concern for the environment due to high production volume (i.e., fossil fuel consumption), often short usage time, and problems related to waste management and accumulation in the natural environment. Creating a circular economy for polyolefins through effective recycling technologies has the potential to decrease the environmental impact of these materials. This perspective discusses polyolefins and their impact, existing and emerging recycling/upcycling solutions, and recycle‐by‐design alternatives that are challenging the status quo. [ABSTRACT FROM AUTHOR]

Maleic anhydride‐grafted‐polyethylene was dynamically cross‐linked via reactive melt blending with 4,4′‐dithiodianiline. Thermal and mechanical properties of polyethylene vitrimers with different cross‐linking density were investigated. The results indicate that the degree of crystallinity decreased with increasing cross‐linking density. This behavior was directly related to short‐term and long‐term mechanical properties: vitrimers showed a decrease in yield strength and creep performance. The yield strength of PE vitrimers decreased linearly in relation to the degree of crystallinity. Polarized optical microscopy revealed that the cross‐links inhibit the growth of spherulites structure in polyethylene vitrimers. Thermogravimetric analysis indicated an increase in the onset degradation temperature and decomposition rate for vitrimers with increased cross‐linking density. The stiffness of the vitrimers decreased with increasing cross‐linking density which led to higher damping properties. Finally, it was demonstrated that reprocessing of polyethylene vitrimer was possible without significant impact in mechanical properties. [ABSTRACT FROM AUTHOR]

Polyolefins have traditionally been polymerized via the heterogeneous Ziegler Natta (Z‐N) catalysts since their discovery in the 1950s, but the later developments of the homogeneous single site metallocene/methylaluminoxane (MAO) catalysts have opened the possibility for the synthesis of polyolefin polymers and copolymers (commercialized in the 1990s) with highly defined microstructure and great degree of control of their molecular architecture resulting in some unique beneficial properties compared to their Z‐N counterparts. The main aim of the work reported here was to examine critically the effects of the processing conditions during multipass extrusions on the molecular and rheological characteristics of metallocene‐catalyzed linear low density polyethylene and a Ziegler‐Natta‐based counterpart polymer and on the thermoxidative (in the melt) stability of their melts and their stabilization. Both polymers examined here were based on ethylene‐1‐hexene copolymers and produced by the same manufacturer with similar density and melt index (MI) values. The melt stability and rheological properties of the polymers were determined from melt flow and capillary rheometric measurements. The molecular characteristics were investigated using GPC for molecular weight determination, 13C‐NMR for short chain branching, 1H‐NMR and FTIR for the type and concentration of unsaturation groups, FTIR for carbonyl‐containing compounds and chemical analysis for hydroperoxide determination. The processibility of the two polymers was compared through examination of different processing conditions (die temperatures 210–285°C, screw speeds 50–200 rpm) used for a multipass extrusion process. Further, the effects of the processing conditions on the melt thermoxidation of the differently catalyzed LLDPE polymers were investigated. The results demonstrated that both the catalyst type and the processing conditions have a great effect on both the rheological and the themoxidative behavior of the polymers as well as on the balance between the competing oxidative reactions taking place in the polymer melt, for example, chain scission and crosslinking reactions. The results obtained for the different multipass extrusion conditions of the two polymers have illustrated clearly that the degradation mechanisms during their melt processing are substantially different. The melt degradation route of the Ziegler‐catalyzed polymer was shown to be dominated by chain scission reactions under all the processing conditions examined, and more so at the higher shear rates and temperatures. By contrast, the evidence clearly showed that the metallocene‐catalyzed polymer gave rise to crosslinking reactions that predominated even under the more severe processing conditions, that is, higher temperatures and shear rates. [ABSTRACT FROM AUTHOR]