Impact of Molecular Weight on the Thermal Stability and the Miscibility of Poly(ε-caprolactone)/Polystyrene Binary Blends

Poly(ε-caprolactone) (PCL) and two different molecular weight (6K and 650K) of polystyrene (PS) were mixed in solution to prepare binary blends of PCL/PS with various compositions. The impact of the molecular weight of PS in the blends was studied on thermal stability and miscibility by the thermogravimetric analysis (TGA) and the differential scanning calorimetry (DSC) method. The TGA results under dynamic conditions in an inert atmosphere show that the thermal stability of the blends depends on the length of PS molecules. The increase of the low molecular weight PS into the PCL/PS blend reduces the thermal stability while the high molecular weight PS improves the thermal stability. The crystallization peak temperature, enthalpy, and crystallinity of the blends are found molecular weight dependent; these parameters with blend compositions deviate from linearity of additive law for low molecular weight PS, while they do follow the additive law for high molecular weight PS. A significant melting point depression of PCL crystals with composition was observed for the blends with the incorporation of the low molecular weight PS, while the no significant melting temperature depression was observed for the high molecular weight PS. The experimental results clearly indicate that in the PCL/PS blends, the thermal stability and the interaction between the neat components strongly depend on the molecular weight of the PS.