Unraveling the complex polymorphic crystallization behavior of the alternating copolymer DMDS-alt-DVE

[Abstract]: A complex crystallization behavior was observe the alternating copolymer DMDS-alt-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 − Tm, and high melting, H − Tm phase. Remarkably, the H − Tm form was only achieved by the previous formation and melting of the L − Tm 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 − Tm). 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 esulting morphological differences can have significant implications and potential impact on mechanical resistance and barrier roperties.Gobierno Vasco; IT1503-22Gobierno Vasco; IT-1525-22Ministerio de Ciencia e Innovación; PGC2018-094620-A-I00Xunta de Galicia; ED431F 2021/00