Effect of chain blockiness on the phase behavior of ethylene‐octene copolymer blends

New challenges and opportunities for polyolefin blends arise from the recent introduction of olefin block copolymers (OBCs). In this study, the effect of chain blockiness on the miscibility and phase behavior of ethylene‐octene (EO) copolymer blends was studied. Binary blends of two statistical copolymers (EO/EO blends) that differed in comonomer content were compared with blends of an EO with a blocky EO copolymer (EO/OBC blends). The blends were rapidly quenched to retain the phase morphology in the melt and the phase volumes were obtained by atomic force microscopy (AFM). Two EOs of molecular weight about 100 kg/mol were miscible if the difference in octene content was less than about 10 mol % and immiscible if the octene content difference was greater than about 13 mol %. The blocky nature of the OBCs reduced the miscibility and broadened the partial miscibility window of the EO/OBC blends compared with the EO/EO blends. The EO/OBC blends were miscible if the octene content difference was less than 7 mol % and immiscible above 13 mol % octene content difference. It was also found that the phase behavior of EO/OBC blends strongly depended on blend composition even for constituent polymers of about the same molecular weight. Significantly more demixing was observed in an OBC‐rich blend (EO/OBC 30/70 v/v) than in an OBC‐poor blend (EO/OBC 70/30 v/v). An interpretation based on extractable fractions of the OBC described the major features of the EO/OBC (30/70 v/v) blends. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1554–1572, 2009