CrystallizationKinetics, Crystallization and MeltingLines of Deuterated and Hydrogenous Isotactic Polybutene‑1

The kinetics of crystallization, lamellar long period, and melting temperatures (<i>T</i>_m) of hydrogenous isotactic polybutene-1 (hPB-1) and its fully deuterated counterpart (deuterated isotactic polybutene-1, dPB-1) with similar molecular weight at different isothermal crystallization temperatures (<i>T</i>_c) were investigated by means of fast scanning chip calorimetry and synchrotron microfocus small-angle X-ray scattering techniques. The Hoffman–Weeks plot where <i>T</i>_m was plotted as a function of <i>T</i>_c was used to determine the equilibrium melting point by extrapolating the data to <i>T</i>_m = <i>T</i>_c. Moreover, following the Gibbs–Thomoson equation and Strobl’s multistage crystallization model, the melting line and crystallization line where <i>T</i>_m or <i>T</i>_c is plotted as a function of inversed lamellar long period (1/<i>d</i>_ac) were constructed to determine the equilibrium melting temperature and equilibrium crystallization temperature by extrapolating the corresponding lines to infinite lamellar long period. The hPB-1 displays faster crystallization rates across the entire temperature range, suggesting a higher supercooling driving its crystallization than in dPB-1. However, hPB-1 possesses a lower equilibrium melting point/temperature but a higher equilibrium crystallization temperature than dPB-1. This peculiar isotope effect on the crystallization behavior of isotactic polybutene-1 provides a unique example supporting the crystallization mechanism proposed by Strobl where the supercooling with respect to the equilibrium crystallization temperature determines the crystallization kinetics.