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The solubility of different alkanes in polyethylene (PE) of different densities, as well as the solubility of the polymers in the alkanes, and the degree of swelling of the powders are studied as a function of temperature. It is found that the solubility of linear low-density polyethylene (LLDPE) is as much as 6 times greater than that of high-density polyethylene (HDPE) at the same temperature, and that LLDPE swells at least 50% more than HDPE the same diluent at the same temperature. The breakthrough curves also show that lighter alkanes swell the PE more at a given temperature than heavier ones. Also, the breakthrough points (the temperature at which the swelling versus temperature curves change slope) occur at lower temperatures for PE of lower density. Gel formation is observed for medium and low density polyethylenes in pentane and hexane. This quantitative information will be useful in developing process models for different industrial polymerization processes, as particle swelling can have a significant impact on slurry viscosity and the flow stability and solids loading of commercial reactors.

It is well known that ultra‐high molecular weight polyethylene (UHMWPE) is a polymer with long chains and very high molecular weight that poses difficulties in terms of processability due to the presence of chain entanglements. In many cases is thus necessary to treat the material in different ways after the polymerization to minimize the amount of entanglements and improve the processability. Based on observations that the use of inert condensing agents (ICA) had a noticeable impact on molecular weight and crystallinity, it was decided to develop a gas‐phase polymerization process with addition of ICA for UHMWPE with a high fraction of disentangled chains. For the optimization of this process, the comparison with slurry is important for the understanding the improvement. Thus, a clear difference between slurry and gas phase is observed in terms of crystallinity and the lamellar thickness of the crystals, molecular weight and entanglements. Characterization techniques are developed to measure the properties of the reactor powder and understand the impact of the alkanes in situ. Using solid‐state drawability, the entanglement degree of the reactor powder is analyzed. From the small‐angle x‐ray scattering and wide‐angle x‐ray scattering techniques, it is possible to find a correlation of entanglements and lamellar thickness. Moreover, crystallization kinetics measurements of the polymer in presence of ICA constitutes a powerful method to explain the phenomena of entanglement and crystal formation.