High-density polyethylene (HDPE) was modified by the grafting of polydimethylsiloxane (PDMS) through a free-radical process, in a melt-mixer chamber, using dicumyl peroxide (DCP) as an initiator. The influence of PDMS (0.2–0.8 mol %) and peroxide (0.03–0.08 mol %) concentrations on the grafting, final torque, and melt flow rate (MFR) of copolymers were investigated using factorial planning. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), MFR, and rheometry were used to characterize the copolymers obtained. Surface plots showed that higher degrees of grafted PDMS and higher final torques were obtained with increase in the PDMS amount at low DCP levels and with increase in the DCP amount at low PDMS levels. The peaks of fusion and crystallization of the copolymers showed no significant changes with respect to HDPE. Data of MFR and GPC suggested that crosslinking reactions and/or chain extension occurred concomitant with the grafting reactions. Copolymers with high grafting degrees showed high MFR and low dynamic shear viscosities in comparison with low grafting degree copolymers, which is probably due to the migration of the PDMS-containing copolymers on the surface.
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