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

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 dimer...

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Detalles Bibliográficos
Autores: Michell Uribe, Rose Mary Rita|||0000-0002-8317-6663, Ladelta, Viko, da Silva, Edgar, Müller, Alejandro J., Hadjichristidis, Nikos
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:dnet:upcommonspor::5caf07ad42c9efa343d6cc0d9d253929
Acceso en línea:https://hdl.handle.net/2117/461834
https://dx.doi.org/10.1016/j.progpolymsci.2023.101742
Access Level:acceso abierto
Palabra clave:Lactides
Polylactides
Stereocomplexes
Synthesis
Macromolecular architecture
Crystallization
Àrees temàtiques de la UPC::Enginyeria dels materials
Descripción
Sumario: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.