Thermally‐Induced Phase Transitions in the Uniaxially‐Oriented δ Form of Syndiotactic Polystyrene

Abstract

AbstractThe empty δ (δe) form of uniaxially‐oriented syndiotactic polystyrene (sPS) samples were obtained by extracting the solvent molecules from the δ form of sPS and solvent complex in acetone and methanol. Temperature dependence of the X‐ray fiber diagrams starting from the uniaxially‐oriented δe and δ form has been measured successfully at various temperatures for the first time. The transition behavior was traced clearly by separating the equatorial and layer line reflections. The δe form transformed to the γ form via an intermediate form. The intermediate form is speculated to take disordered structure due to the empty cavities present in the δe form. Calorimetric studies showed an endotherm followed by an exotherm during this phase transition, which is consistant with such a speculation. On the other hand the δ form transformed to the γ form directly without passing through the intermediate form or δe form. During the δ to γ phase transition the solvent molecules evaporate through the columnar structure in a broad range of temperature, allowing the transition to occur smoothly.