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Synthesis and characterization of pullulan-graft-poly (N-vinyl caprolactam) via RAFT/MADIX polymerization

Lari, Atefe Sadeghi, Silva, Gabriela Aparecida Braga, Alves, Gizelda Maria, Bergeron-Brlek, Milan, dos Santos, Amilton Martins et Demarquette, Nicole Raymonde. 2026. « Synthesis and characterization of pullulan-graft-poly (N-vinyl caprolactam) via RAFT/MADIX polymerization ». Materials Today Communications, vol. 56.

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Résumé

This study presents a novel synthetic strategy for preparing graft copolymers based on a pullulan backbone. The approach relies on reversible addition-fragmentation chain transfer (RAFT) radical polymerization as the key step. This significant advancement enables the synthesis of the temperature-responsive copolymer pullulan-graft-poly(N-vinyl caprolactam) (PULL-g-PNVCL), leveraging the renewable, biocompatible, and biodegradable nature of pullulan to access this previously challenging target. The synthesis involved partial functionalization of pullulan with bromopropionyl bromide, followed by substitution with a pre-synthesized xanthate-based chain transfer agent, and subsequent polymerization of N-vinyl caprolactam from the pullulan macro-chain transfer agent. Comprehensive characterization, including Gel Permeation Chromatography (GPC) and Proton Nuclear Magnetic Resonance spectroscopy (1H NMR), confirmed successful graft copolymerization. The results showed decreased thermal stability of PULL-g-PNVCL compared to pullulan. Dynamic light scattering (DLS) analyses demonstrated a thermosensitive behavior, with particle diameter increasing upon surpassing the lower critical solution temperature (LCST) of PULL-g-PNVCL. The LCST was observed to vary as a function of the poly(N-vinyl caprolactam) chain length. The obtained LCST values were lower than physiological temperature, which embeds PULL-g-PNVCL with the potential for expanding pullulan applications, particularly in biomedical fields such as stimuli-responsive drug delivery systems. Integrating chemical principles with polymer design, this research showcases the development of bio-based functional materials, an objective aligned with the sustainable use of industrial crops.

Type de document: Article publié dans une revue, révisé par les pairs
Chercheur(-euse):
Chercheur(-euse)
Bergeron-Brlek, Milan
Demarquette, Nicole R.
Affiliation: Département des enseignements généraux, Génie mécanique
Date de dépôt: 25 sept. 2026 20:42
Dernière modification: 27 sept. 2026 18:44
URI: https://espace2.etsmtl.ca/id/eprint/34436

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