Abstract: | This study was concerned with the structural features and mechanical properties of polypropylene (PP)/low‐density polyethylene (LDPE) blends, which after compounding were modified by the free‐radical grafting of itaconic acid (IA) to produce PP/LDPE]‐g‐IA in the course of reactive extrusion. To analyze the structural features of the PP/LDPE]‐g‐IA systems, differential scanning calorimetry and relaxation spectrometry techniques were used. The data were indicative of the incompatibility of PP and LDPE in the PP/LDPE]‐g‐IA systems on the level of crystalline phases; however, favorable interactions were observed within the amorphous phases of the polymers. Because of these interactions, the crystallization temperature of PP increased by 5–11°C, and that of LDPE increased by 1.3–2.7°C. The rapprochement of their glass‐transition temperatures was observed. The single β‐relaxation peak for the PP/LDPE]‐g‐IA systems showed that compatibility on the level of structural units was responsible for β relaxation in the homopolymers used. Variations in the ratios of the polymers in the PP/LDPE]‐g‐IA systems led to both nonadditive and complex changes in the viscoelastic properties as well as mechanical characteristics for the composites. Additions of up to 5 wt % PP strengthened the PP/LDPE]‐g‐IA blended systems between the glass‐transition temperatures of LDPE and PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1746–1754, 2006 |