Temperature-Dependent Triple Crystal Polymorphism of Poly(hexamethylene terephthalate): Long-Range Ordered Mesophase Formation and Crystal Structure–Property Relationships

Terephthalic polyesters are important engineering plastics and can crystallize into multiple crystal phases, including the mesophase in processing. However, the formation process and structural characteristics for the unique long-range ordered mesophase of terephthalic polyesters are still not well understood. Herein, we investigated the crystal polymorphism, crystallization kinetics, phase transition, and mechanical properties of a medium-chain terephthalic polyester, poly(hexamethylene terephthalate) (PHT). A new long-range ordered mesophase (named as the δ phase) is discovered for PHT during quiescent melt crystallization at a low crystallization temperature (Tc = 10–30 °C). However, the α and β crystal phases are crystallized at a medium (40–80 °C) and high (90–130 °C) Tc, respectively. The mesomorphic δ phase has a long-range order with a layered structure and inclined chain packing, which shows faster chain relaxation and smaller lamellar thickness than the α and β phases. The mesomorphic δ phase is metastable and converts into the stable β phase upon heating or high-temperature annealing. Mechanical properties of PHT can be well tuned by crystal polymorphs. The mesomorphic δ phase of PHT has good transparency and ductility, while the α and β phases possess a higher yield strength and modulus. This work provides an in-depth understanding of the mesophase formation and complex crystal polymorphism of terephthalic polyesters.