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Hindered amine light stabilizers (HALS) are widely used chemical stabilizers for preventing polymer degradation. In this study, the effects of type of HALS and its content in high‐density polyethylene (HDPE) over the stabilization process are investigated employing density functional theory (DFT) and experimental approach. The electrophilicity index of four types of commercial HALS are compared by DFT to select the most effective one. Besides, the HDPE sample containing a phenolic antioxidant and different contents of the selected HALS are experimentally exposed to UV irradiation. The effect of HALS content on the changes in chain microstructure and molecular weight of HDPE are evaluated using gel permeation chromatography and frequency sweep rheometry. In the absence of HALS, HDPE suffers degradation and the phenolic antioxidant causes chain scission. However, by adding HALS, the chain branching and crosslinking mechanisms are predominant. The results of FTIR, DSC, and tensile analyses follow similar trends, revealing that the best stabilization performance corresponds to adding 600 ppm HALS to HDPE.

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