Miscibility, phase diagrams and morphology of poly(ε-caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene-co-acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed-loop miscibility window. DSC showed only one glass transition temperature (T g ) for PCL/PBzMA/SAN-17 and PCL/PBzMA/SAN-25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN-17 and PCL/PBzMA/SAN-25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN-17 and PCL/PBzMA/SAN-25 ternary blends, but that the ternary system becomes phase-separated outside these AN contents.
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