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Updated: Jul 11, 2025

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Crystal Polymorphism of Isodimorphic Polyesters Tuned by cis- and trans-C═C Comonomer Units
Xuekuan Ma1, Xuanbo Wang1, Chenxuan Sun1
1State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, China.
Abstract:
Polymorphism is ubiquitous in polymer crystallization due to the diversified chain conformations and interchain packings in polymer crystals. Controlling chain conformation is effective in tailoring the crystal polymorphism of polymers, which, however, is challenging at the molecular level. Herein, we have synthesized poly(butylene adipate) (PBA)-based copolymers containing C═C units and demonstrated the important role of trans/cis-C═C units in tuning the chain conformation and crystal polymorphism of polymers. Both PBA-based trans- and cis-copolymers show isodimorphic crystallization behavior with the partial inclusion of C═C units in PBA crystals. The presence of trans-C═C units favors the formation of metastable β-crystals of PBA and retards the β-to-α crystal transition upon heating due to the highly conformational matching between trans-C═C units and β-crystals. Conversely, the incorporation of cis-C═C units destroys the regularity of the trans conformation and favors the growth of α-crystals of PBA. This work has elucidated the crucial role of local chain conformation in the crystal polymorphism of polymers.
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