Controllable Poly(Silicone‐Ester) Segments‐Enhanced Thermodynamic Compatibility for Thermoplastic Polyurethane

ABSTRACT Thermoplastic silicone‐ester polyurethane (TSPU) has garnered significant attention due to its distinctive combination of inorganic silicone and organic polyester. However, conventional thermoplastic silicone polyurethanes often suffer from inadequate mechanical strength, primarily due to poor thermodynamic compatibility. In this work, we address this challenge by enabling the controllable incorporation of soft segments (SS) into TSPU. A bulk‐solution polymerization approach was employed to synthesize a series of novel TSPUs. The results reveal that these TSPUs exhibit tunable copolymerized soft segment sequences with molecular weights ranging from 0.86 × 10 4 to 1.26 × 10 4 g mol −1 . The inclusion of PDMS is shown to significantly modify the TSPU microstructure, facilitating the formation of three‐phase block sequences, suppressing crystallization, and enhancing microphase separation. Notably, TSPU‐2, comprising PCDL/PDMS in a mass ratio of 8:2, demonstrates superior low‐temperature resistance (−106.5°C), favorable thermal stability (250°C), and remarkable flexibility (14.2 MPa tensile strength, 429% elongation). This study provides valuable insights into the structure–property relationships in TSPUs, contributing to the development of advanced materials tailored for demanding application scenarios.