Biobased block copolymers: self-assembly and hierarchical polymer morphologies

Biobased block copolymers: self-assembly and hierarchical polymer morphologies

We are pleased to share our latest publication in Biomacromolecules (ACS Publications), focused on the design and self-assembly of biobased block copolymers and their hierarchical structures.

This work represents the final part of the PhD thesis of our former student Flore Kilens, who played a central role in the development of this research together with Lucas Polo Fonseca. The study is the result of a collaboration between the research group of Andrew Dove at the University of Birmingham, the groups of Alejandro J. Müller and Haritz Sardon at the University of the Basque Country (EHU), and the team at POLYKEY.

A key objective of this work was to understand how biobased block copolymers organize at the nanoscale and how their molecular architecture influences self-assembly. By tuning segregation strength and thermal history, we demonstrate that these systems can form well-defined and highly ordered structures, including body-centered cubic spherical phases and lamellar structures with long-range order. These results highlight how molecular design governs crystallization and phase behavior, leading to hierarchical morphologies.

The study shows that small variations in polymer architecture lead to significant differences in phase behavior, crystallization, and final material properties. In particular, biobased block copolymers exhibit a strong coupling between crystalline and amorphous domains, which governs the emergence of hierarchical structures and enables precise control over material performance.

Beyond fundamental insights, this work demonstrates the potential of biobased block copolymers for the development of high-performance, fully renewable polymer systems, with applications in sustainable thermoplastics, biodegradable materials, and advanced polymer engineering.

This research was carried out thanks to the contribution of Flore Kilens, Lucas Polo Fonseca, Ane Olazabal Abarrategui, Leire Unanue, Jorge Luis Olmedo Martínez, Monika Król, Daniele Mantione, Natalia Reis, Andrew Dove, Haritz Sardon Muguruza, Alejandro J. Müller, and Coralie Jehanno, and reflects the strength of the collaboration between all participating institutions.