Cold crystallization of polytrimethylene terephthalate and copolymers

The melt of crystalline polymers normally crystalize on cooling and the polymer melts with low critical cooling rate would easily solidify as glass during cooling to their glass transition temperature (T_g). The glassy process exhibits variety within each kind of polymer melts in the slope of the viscosity-temperature visibility, and the rate of the excess conformational entropy in the polymer melt over the crystalline phase changes in the T_g approaching. Polytrimethylene terephthalate (PTT) and a series of polytrimethylene terephthalate copolyesters (PTTG) with different molar ratios of 1,3-propylene glycol (1,3-PDO) to 1,4-cyclohexanedimethanol (1,4-CHDM) were synthesized to modify the chain flexibility and the critical cooling rate. The glassy samples were obtained via quenching the melts of PTT and copolymers below the T_g to characterize the cold crystallization behaviors. The evolutions of the crystalline structure of the amorphous samples were in situ investigated via DSC and simultaneous WAXS/SAXS approaches during heating. The polymer chain dynamics and the critical cooling rates of the PTT and copolymers were estimated by rheological testing and DSC characterization. The results indicate that the chain conformation adjustment of PTT and copolymers is relate to the comonomers in the copolymers, and the cold crystallization behaviors can be divided into three temperature ranges during heating. The first involves rapid transition from a pre-ordered phase to a crystalline phase, the second is the adjustment of defects in an imperfect crystalline phase, and the third may refer crystal reorganization before melting. The crystallization ability of the samples could be due to the ability of chain conformation adjustment with comonomer content till the crystallization is no longer obvious during heating. The cold crystallization behaviors of the samples were discussed based on the polymer chain dynamics and it is convinced that would be helpful to understand the crystallization and processing of polymers.