Poly(lactic acid) stereocomplexes based molecular architectures: Synthesis and crystallization

Rose Mary Michell, Viko Ladelta, Edgar Da Silva, Alejandro J. Müller*, Nikos Hadjichristidis*

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

5 Scopus citations


This review presents the state of the art of complex macromolecular architectures based on polylactide stereocomplexes (PLA-sc) from the viewpoint of synthesis and crystallization. First, we discuss the nomenclature, synthesis, epimerization, and lactide (LA) properties as a bio-derived cyclic dimeric monomer comprising two chiral carbons. Among several polymerization methods, catalytic ring-opening polymerization (ROP) is the most common and versatile technique to access stereoregular (isotactic) PLA, which is the prerequisite to preparing PLA-sc. Combined with other living and controlled/living polymerization techniques, ROP of LA has yielded various PLA-sc-based macromolecular architectures, including copolymers, stars, graft, cyclic, brush, and hybrid materials. New approaches to synthesizing monodisperse discrete oligoLA are also discussed. We show that a small change in the architectures, microstructures, molecular weight, or other chemical and physical modifications affects the behavior of PLA-sc. Moreover, the crystallization of PLA-sc, after more than 30 years of study, still presents many challenges. The crystalline morphology is also a subject of debate. Recent findings suggest a new crystalline unit cell for PLA-sc. Adding a third component or changing chain architecture can significantly modify the properties of the formed PLA-sc. The complex relationship between flexibility, nucleation, diffusion, and the interactions needed for the joint crystallization of the enantiomers constitutes a very large source of variables. As a result, PLA-based stereocomplex materials can be tailored by manipulating one or several of these variables.

Original languageEnglish (US)
Article number101742
JournalProgress in Polymer Science
StatePublished - Nov 2023

Bibliographical note

Publisher Copyright:
© 2023 The Author(s)


  • Crystallization
  • Lactides
  • Macromolecular architecture
  • Polylactides
  • Stereocomplexes
  • Synthesis

ASJC Scopus subject areas

  • Ceramics and Composites
  • Surfaces and Interfaces
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry


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