Thermoplastic polyurethane (TPU) has become a pivotal engineering material due to its unique combination of elasticity and processability. Recent research has focused on elucidating the structure-property relationship to guide high-performance TPU design. This study innovatively explores the impact of segment sequence length on material performance through a systematic synthesis strategy. Using pre-polymerization and chain extension techniques
we developed a series of hydrazide-based TPU elastomers with identical hard/soft segment ratios but varying sequence lengths. Characterization results reveal that extending the sequence lengths induces two critical structural modifications: enhanced microphase separation between hard and soft domains
and optimized hierarchical hydrogen bonding networks. These structural changes collectively elevate material performance
with long-sequence TPUs exhibiting a 50% increase in tensile strength (from 50 MPa to 80 MPa)
and significantly higher flow temperatures (ΔT >45 °C) compared to short-sequence counterparts. Notably
stress relaxation tests demonstrate that extended sequences increase the relaxation time significantly
indicating superior dimensional stability. The performance enhancements stem from the dual reinforcement mechanism: microphase separation creates robust physical crosslinks while hierarchical hydrogen bonds enable energy dissipation. This sequence engineering approach provides a paradigm shift from traditional composition-focused design to topological structure optimization
offering a viable pathway for developing TPUs that simultaneously satisfy conflicting requirements of mechanical robustness and processing efficiency in industrial applications.
College of Chemical Engineering, Jiangxi Normal University
Engineering Research Center of Eco-friendly Polymeric Materials (MoE), National Engineering Laboratory of Eco-Friendly Polymeric Materials, College of Chemistry, Sichuan University