Effect of Annealing Process and Molecular Weight on the Polymorphic Transformation from Form II to Form I of Poly(1-butene)

Abstract

Poly(1-butene) (PB-1) resin has excellent mechanical properties, outstanding creep resistance, environmental stress crack resistance and other excellent properties. However, PB-1 resin experiences a crystal transformation for a period, which seriously affects the production efficiency and directly restricts its large-scale commercial production and application. The factors affecting the crystal transformation of PB-1 are mainly divided into external and internal factors. External factors include crystallization temperature, thermal history, nucleating agent, pressure, solvent induction, etc., and internal factors include chain length, copolymerization composition, isotacticity, its distribution, etc. In this study, to avoid the interference of molecular weight distribution on crystallization behavior, five PB-1 samples with narrow molecular weight distribution (between 1.09 and 1.44) and different molecular weights (from 23 to 710 k) were chosen to research the influence of temperature and time in the step-by-step annealing process and molecular weight on the crystal transformation by differential scanning calorimetry (DSC). When the total annealing time was the same, the step-by-step annealing process can significantly accelerate the rate of transformation from crystal form II to I. PB-1 samples with different molecular weights have the same dependence on annealing temperature, and the optimal nucleation temperature (i.e., low annealing temperature, Tl) and growth temperature (i.e., high annealing temperature, Th) were −10 °C and 40 °C, respectively. At these two temperatures, the crystal form I obtained by step-by-step annealing had the highest content; other lower or higher annealing temperatures would reduce the rate of crystal transformation. When the annealing temperature was the same, crystal form I first increased with annealing time tl, then gradually reached a plateau, but the time to reach a plateau was different. The crystalline form I contents of the samples with lower molecular weight increased linearly with annealing time th. However, the crystalline form I contents of the samples with higher molecular weight increased rapidly with annealing time th at the beginning, and then transformation speed from form II to form I slowed down, which implied that controlling Tl/tl and Th/th can tune the different contents of form I and form II. At the same Tl/tl or Th/th, with increasing molecular weight, the transformation speed from form II to form I via the step-by-step annealing process firstly increased and then slowed down due to the competition of the number of linked molecules and molecular chain mobility during crystallization. This study definitely provides an effective method for accelerating the transformation of poly(1-butene) crystal form, which not only has important academic significance, but also has vital industrial application.