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Unique Hierarchical Mesostructures Arising from Biobased Double-Crystalline PLLA-b-PHDO-b-PLLA ABA Triblock
Flore Kilens1,2,3, Lucas Polo Fonseca2,4, Ane Olazabal1,2
1POLYKEY POLYMERS, Avenida de Tolosa 72, San Sebastian 20018, Spain.
Biomacromolecules
|June 16, 2026
Summary
This study created fully biobased triblock copolymers using organocatalyzed polycondensation and ring-opening polymerization. These materials exhibit tunable morphologies and potential for self-supporting films with tailored properties.
Area of Science:
- Polymer Science
- Materials Science
- Sustainable Chemistry
Background:
- Block copolymers (BCPs) self-assemble into microphases, enabling tailored material properties.
- Developing fully biobased BCPs is crucial for sustainable materials.
- Controlling self-assembly is key to achieving desired material structures and functions.
Purpose of the Study:
- To synthesize fully biobased ABA triblock copolymers using poly(1,6-hexanediol) (PHDO) and poly(l-lactide) (PLLA).
- To investigate the structure-morphology relationships influenced by segregation strength (χN).
- To explore the potential of these biobased BCPs for film formation and property evaluation.
Main Methods:
- Combined organocatalyzed polycondensation and ring-opening polymerization (ROP).
- Varied segregation strength (χN) from 4 to 11.
- Analyzed morphology evolution with changes in χN and thermal history.
Main Results:
- Achieved fully biobased ABA triblock copolymers of PHDO and PLLA.
- Observed a transition from weak to intermediate segregation with increasing χN.
- Identified long-range order and body-centered cubic (BCC) spherical morphology at χN ≥ 6.
- Obtained distinct hierarchical structures (BCC spheres, BCC plus lamellar, interdigitated double-lamellar) based on thermal history.
- Formed self-supporting films from BCPs with higher PLLA molar mass (18.5 kDa).
Conclusions:
- Established structure-morphology relationships for fully biobased double-crystalline triblock copolymers.
- Demonstrated the tunability of morphology through segregation strength and thermal history.
- Highlighted the potential of these biobased materials for advanced applications, including self-supporting films.
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