Unraveling the Complex Polymorphic Crystallization Behavior of the Alternating Copolymer DMDS-alt-DVE

[Image: see text] A complex crystallization behavior was observed for the alternating copolymer DMDS-alt-DVE synthesized via thiol–ene step-growth polymerization. Understanding the underlying complex crystallization processes of such innovative polythioethers is critical for their application, for example, in polymer coating technologies. These alternating copolymers have polymorphic traits, resulting in different phases that may display distinct crystalline structures. The copolymer DMDS-alt-DVE was studied in an earlier work, where only two crystalline phases were reported: a low melting, L – T(m), and high melting, H – T(m) phase. Remarkably, the H – T(m) form was only achieved by the previous formation and melting of the L – T(m) form. We applied calorimetric techniques encompassing seven orders of magnitude in scanning rates to further explore this complex polymorphic behavior. Most importantly, by rapidly quenching the sample to temperatures well below room temperature, we detected an additional polymorphic form (characterized by a very low melting phase, denoted VL – T(m)). Moreover, through tailored thermal protocols, we successfully produced samples containing only one, two, or all three polymorphs, providing insights into their interrelationships. Understanding polymorphism, crystallization, and the resulting morphological differences can have significant implications and potential impact on mechanical resistance and barrier properties.