Structure and properties of the mesophase of syndiotactic polystyrene. I. Effect of casting conditions on the preparation of the mesophase

A syndiotactic polystyrene–toluene solution was cast under two different casting conditions to obtain the δ form. A systematic study of its conformational transition, thermal behavior, and structural transformation as functions of the annealing temperature and time was performed. Spectroscopic studies revealed the content of its helical conformations and its retention up to 190 °C. Thermal analyses showed a significant difference in the transformation from the γ form to the α form. The retention of the intermediate emptied clathrate form (mesophase) of the conformational order for a longer duration (from 120 to 180 °C) in a syndiotactic polystyrene membrane cast at room temperature was confirmed by X‐ray diffraction analysis. On the basis of the experimental results in this work, the transition mechanism is discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 530–536, 2002; DOI 10.1002/polb.10120