Progressive Relaxation Behavior and Relaxation Dynamics of sPS Gels upon Controlled Heating.

Progressive relaxation behavior of syndiotactic polystyrene (sPS) chains in sPS gel was detected in the course of melting via the application of intrinsic fluorescence and fluorescence anisotropy techniques. The melting process included a dissociative process of the network at lower temperature and a relaxation process from helix to worm-like chains at higher temperature. The dynamics of structural relaxation behavior was discovered by intrinsic fluorescence technique, and an abrupt bend emerged at 58 °C on the Arrhenius plot. At temperatures lower than 58 °C, only the dissociation of the helical structure existed and the rate of relaxation from helix to worm-like conformation was negligible. At temperatures higher than 58 °C, the transition from helical chain to worm-like chain was the rate-determining step. The intrinsic fluorescence technique demonstrated its practicability in detecting kinetic processes of sPS/chloroform gel in the course of melting.