Abstract
Blends of high‐density polyethylene (HDPE) with novel linear low‐density polyethylene (LLDPE) samples in the whole range of compositions were investigated by means of differential scanning calorimetry (DSC), small‐angle X‐ray scattering (SAXS) and wide‐angle X‐ray diffraction (WAXD). The LLDPEs are ethylene/octene‐1 copolymers prepared with a single‐site catalyst, with a narrower distribution of branches compared to Ziegler‐Natta type polymers. It was found that cocrystallization or separate crystallization in the blends profoundly depends on the content of branches in the LLDPE, while the critical branch content of the novel LLDPE for separate crystallization is much lower than that of commercial LLDPE (prepared with Ziegler‐Natta catalysts). This implies that the miscibility of linear and branched polyethylene is also affected by the distribution of branches. The marked expansion of the unit cell in cocrystals, which are formed by HDPE with the novel LLDPE, indicates that the branches are included in the crystal lattice during the cocrystallization process. The result is very helpful to understand the phenomenon that the unit cell dimensions of commercial branched polyethylene are larger than those of linear polyethylene.