Structure, morphology and crystallization of isodimorphic random copolymers: Copolyesters, copolycarbonates and copolyamides

Abstract

Random copolymerization is used to prepare new polymeric materials that combine the desirable properties of different homopolymers. The covalent bonds between the comonomers enable miscibility and the formation of random copolymers with specific properties tailored for various applications. The crystallization behavior of random copolymers is intricate, encompassing up to three crystallization modes, i.e., total comonomeric exclusion, isomorphism, and isodimorphism. Isomorphism and isodimorphism allow for crystallization across the entire composition range, resulting in unique and potentially advantageous properties for each composition. These characteristics have garnered significant attention, as evidenced by the multiple publications that have appeared in the last decade.This contribution reviews the progress made in several aspects of isodimorphic copolymers, including new cases and applications. The initial section focuses on the factors influencing the pseudo-eutectic position, which is crucial for understanding the crystallization behavior of these copolymers. Subsequently, advancements in determining the degree of comonomer inclusion are discussed. Another section highlights studies that have raised new questions about the concepts of isodimorphism and isomorphism, particularly their presence in blends and terpolymers. These findings have opened up new avenues for research.In the final part of this review, selected examples are presented to illustrate the relationship between structure and properties in random copolymers. Furthermore, practical applications, such as using random copolymers as hot melt adhesives, are showcased. Despite significant progress in understanding the crystallization modes in random copolymers, this contribution emphasizes that new phenomena continue to emerge, providing further opportunities for exploration and shedding light on novel applications related to these intriguing crystallization modes.