Influence of trimodal polymerization on melt rheology, thermal, and mechanical properties of HDPE resin

Abstract Trimodal polymerization of polyethylene has become a research interest in recent years due to its excellent potential for altering material properties and overcoming the limitations of the bimodal process. Here, we have comprehensively investigated the effects of manipulating polymerization parameters, such as split value (SV), hydrogen‐to‐ethylene ratio (H 2 /C 2 ), and stage switching, on the rheological, thermal, and mechanical properties of synthesized trimodal high‐density polyethylene (HDPE). The synthesized samples were obtained through three consecutive stages in a slurry lab‐scale reactor. The results of molten state analysis demonstrate that recipe modification, particularly SV and H 2 /C 2 balancing in the second and third stages, had a dramatic effect on the rheological properties including dynamic moduli, G′‐G″ crossover, and the shear‐thinning behavior. Concurrently, improvements in physio‐mechanical properties, such as sagging behavior and slow crack growth resistance (SCG), were observed compared to the bimodal resin. The thermal characterization indicates that the polymerization adjustments made did not notably impact the thermal properties of HDPE samples (e.g., Tm), throughout the all‐recipe manipulation. However, minor fluctuations in crystallinity and crystallization kinetics were observed which was presumably attributed to the molecular weight of the final resin. Overall, in our trimodal polymerization recipe, the HDPE powder is within the specified range of particle size distribution, which ensures excellent bulk density and flowability. Highlights Influence of polymerization parameters such as split value, H 2 /C 2 , and stage switching in properties of trimodal HDPE. HDPE resin received from split value and H 2 /C 2 balancing have superior SCG and sagging resistance. All HDPE samples synthesized by different recipes have similar thermal properties.